Non-Aqueous Organo Liquid Delivery Systems containing dispersed Poly (organic acids) that improve availability of macro &amp; micro-nutrients to plants

ABSTRACT

The present invention relates to improving the efficiency of man-made and/or natural organic-based animal manure fertilizers by administration of formulations containing poly(organic acids), [P(OA)]s, and/or their salts dispersed in a Non-aqueous Organic Solvent Delivery System (NOSDS). Utilizing a NOSDS allows for coating all components in a fertilizer formulation including but not limited to Urea, Manure, mono-ammonium phosphate (MAP), di-ammonium phosphate (DAP), solid micronutrients such as lime, zinc chloride, etc.) with a layer of [P(OA)]s and/or their salts that liberates, in a plant available form, the micronutrient metals and macronutrients, that are bound as insoluble salts and complexes in the soil. The carboxylic groups of a [P(OA)] that can exist within the [P(OA)] as carboxylic acids, carboxylic anhydrides and/or carboxylic imides, dispersed within the NOSDS, can be neutralized with one or more metals in the form of elemental metals, metal oxides, metal hydroxides, metal alkylates and metal carbonates and/or nitrogen containing compounds such as ammonia, ammonium hydroxide or organoamines to form a stable dispersion that can contain completely complexed micronutrients and provide the vehicle for the delivery of these nutrients to soils and/or as a coating to the surfaces fertilizer granules and seeds.

The present invention claims priority under 35 USC 119(e) and 35 USC 120and is a continuation of U.S. application Ser. No. 15/893,650 filed Feb.11, 2018, which is a continuation of and in turn claims priority to U.S.application Ser. No. 15/079,844 filed Mar. 24, 2016, which in turnclaims priority under 35 USC 119(e) and 35 USC 120 and is a continuationin part of U.S. application Ser. No. 14/740,327 filed Jun. 16, 2015,which claims priority to U.S. Provisional No. 62/160,918 filed May 13,2015, the entire contents of all of which are incorporated by referencein their entireties.

FIELD OF INVENTION

The present invention relates to improving the efficiency of man-madeand/or natural organic-based animal manure fertilizers by administrationof formulations containing poly (organic acids), [P(OA)]s, and/or theirsalts dispersed in a Non-aqueous Organic Solvent Delivery System(NOSDS). Utilizing a NOSDS allows for coating all components in afertilizer formulation including but not limited to Urea, Manure,mono-ammonium phosphate (MAP), di-ammonium phosphate (DAP), solidmicronutrients such as lime, zinc chloride, etc.) with a layer of[P(OA)]s and/or their salts that liberates, in a plant available form,the micronutrient metals and macronutrients, that are bound as insolublesalts and complexes in the soil. The carboxylic groups of a [P(OA)] thatcan exist within the [P(OA)] as carboxylic acids, carboxylic anhydridesand/or carboxylic imides, dispersed within the NOSDS, can be neutralizedwith one or more metals in the form of elemental metals, metal oxides,metal hydroxides, metal alkylates and metal carbonates and/or nitrogencontaining compounds such as ammonia, ammonium hydroxide or organoaminesto form a stable dispersion that can contain completely complexedmicronutrients and provide the vehicle for the delivery of thesenutrients to soils and/or as a coating to the surfaces fertilizergranules and seeds. The metal or metal portions of one of the reactantscan further be defined for this invention as Na, K, Mg, Ca, Fe, Zn, Mn,Cu, Co, Mo, or Ni. Organoamine is one or more of the group consisting ofmono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine,diethanol amine, triethanol amine, monoisopropyl amine, diisopropylamine, triisopropyl amine, diethyl amine, diethylene triamine, triethyltetraamine, tetraethyl pentamine. It has also been discovered that[P(OA)]s and/or their salts can be produced in situ in a NOSDS utilizingorganic acids and/or esters monomers dispersed/suspended within theNOSDS, heated to a polymerization temperature with or without catalystand then neutralized/reacted with one or more macronutrients and/ormicronutrients. The liquid compositions of [P(OA)]s in a NOSDS and themethods to produce a [P(OA] within a NOSDS results in a flowable, lowmoisture liquid that can be readily mixed with liquid fertilizers orapplied safely, quickly, evenly and economically on the surface of solidfertilizer granules, soil and seeds.

BACKGROUND OF THE INVENTION

Macronutrients (N, K, Ca, Mg, P, and S) and Micronutrients (Fe, B, Mn,Zn, Cu, Mo, Co, and Ni) are crucial to a plant's growth, development,disease resistance and various metabolic pathways such asphotosynthesis. Plant available micronutrient insufficiencies are due totraditional farming methods that have exhausted the soil and to themicronutrient metals existing as water insoluble salts and complexes.Many of the water insoluble forms in the soil involve a metal cation andboron, sulfur, or phosphorous based anions. A deficiency inmicronutrients results in poor plant growth and development and thus indiminished yields (Mortvedt 1990). Plant requirements for many of themicronutrients can be as low as parts/million in the plant tissue. It isknown that increasing the plant available micronutrient metal ions byaddition of complexed metal ions to the soil or to plant foliage or byfreeing up micronutrients, bound in the soil as an insoluble salts orcomplexes, in a plant absorbable form can help to significantlyalleviate soil deficiencies and assist in development, growth, anddisease resistance of the plants.

Phosphorous is second to nitrogen as the most limiting macronutrient. Inthe case of phosphorus fertilizer, 40% of landscape soil is consideredto contain inadequate levels of phosphorus for woody plant growth.Moreover, most of the phosphorus in the soil is largely inaccessible asit exists in a form that is not soluble in water and thus is not readilyavailable to plants. In some cases, only 0.01% of the total soilphosphorus is in the form of a water soluble ion, the only form whichcan be absorbed by the plant. Adequate and accessible soil phosphorus isessential for optimal crop yields. Phosphorus enables a plant to storeand transfer energy, promotes root, flower and fruit development, andallows early maturity. Phosphorus is also involved in many processescritical to plant development such as photosynthesis where plantsutilize organic phosphorous compounds when converting sunlight toenergy. Without enough phosphorus present in the soil, plants cannotgrow sufficient root structure, which is key to the plant's ability toabsorb water and nutrients from the soil. Moreover, woody plants,without sufficient root structure cannot maintain an equilibrium betweenroots and shoots, which is key to surviving drought, windy weather,and/or pests. Many of the nutrients required by plants are locked intosalts and complexes that are water insoluble and therefore not plantavailable. To overcome these challenges, the agriculture industry hasturned to chelates and anionic based polymers to form water solublecomplexes with metal cations such as the micronutrients Ca, Mg, Mn, Fe,Cu, Co Ni, Zn, and Mo resulting in freeing up bound macronutrients suchas phosphorous. The current delivery system technology of the chelatesand polymer based products is water. Water is not only an excellentsolubilizing/dispersing medium for chelates and [P(OA)]s, but cansolvate a high load of water soluble metal salts. However, the use ofwater soluble metal salts can form insoluble complexes with chemistriesthat allow them to be available in the soil but unavailable to theplant.

Coating a fertilizer with water based products can result in severeclumping of the fertilizer granules during blending, or gelling of the[P(OA)]s due to high electrolyte content caused by the fertilizergranule dissolving into the water. Clumping has a negative impact on itseffectiveness to complex with metal cations, and/or it requires a dryingstep for seed coatings to prevent pre-mature sprouting or the growth ofmold and mildew, which ultimately destroys the seeds. The use of aqueousbased systems also has a deleterious impact on the urease inhibitorNBPT. The agricultural industry needs a technology that is able toeasily, safely, evenly, and economically coat fertilizer granules andseeds with non-aqueous, liquid formulations that contain [P(OA)]s thatcan form water soluble metal cation complexes and free up boundmacronutrients such as phosphorous.

DESCRIPTION OF RELATED ART

To present, multiple products have been developed to try to:

-   -   Increase the efficiency of the release of macronutrients, such        as phosphorus, from a fertilizer formulation in plant absorbable        form,    -   Release nutrients bound in the soil as insoluble salts and        complexes    -   Deliver a fertilizer formulation that contains micronutrients in        a plant available form.    -   Develop a coating for seeds:        -   that is not water based as high moisture content may be            detrimental to the health and viability of the seed        -   that can delivered desired micronutrients during the seed's            germination        -   that can provide a hydrophilic coating that can act as a            moisture pump to assist in insuring that the seed does not            dry out after distribution on the soil when the external            seed coating has begun to deteriorate allowing moisture to            penetrate to the coating containing [P(OA)] dispersed in the            NOSDS.

The mechanisms of action for the vast majority of these products aresimilar. When a fertilizer containing phosphorus is applied to the soil,most of the phosphorous is in a water-soluble phosphate ion form, theonly form of phosphorus that is readily absorbed by the plant. In thepresence of moisture, however, these soluble phosphate anions can formcomplexes with metal cations such as calcium, magnesium, iron, andaluminum. These salts have very low solubility in water and thus, cannotbe readily absorbed by plants. Polymers with negatively charged ions cancomplex with the metal cations resulting in a freed, water-solublephosphate anion and with the metal cation in a plant available form.Both the phosphate anion and the [P(OA)] complexed cation are now morereadily available to plants for absorption.

Various methods or variations of the above described mechanism arelisted in the patents below, which are incorporated by reference intheir entireties. These methods have been proposed and developed for therelease of nutrients bound in the soil, a delivery system formicronutrients to soil and to seeds and the manufacturing processes toproduce the metal cation complexing [P(OA)]s.

Boehmke (U.S. Pat. No. 4,839,461) teaches how to synthesize and use aman-made version of polyaspartic acid and its salts that preventsincrustations formed by the metal ions that are responsible for hardwater. Boehmke further discloses that this compound can be used as afertilizer.

Ashmead (U.S. Pat. No. 4,172,072) discloses the use of protein sourcesto form metal proteinates, which are in a biologically accepted form.Others reveal carboxylic containing entities either as monomers or aspolymers such as Danzig (U.S. Pat. No. 4,799,953), which utilizespolymers of thiolactic acid or thioglycolic acid and thiolactic acid,dithiobispropanoic acid and dithiobisacetic acid, Kinnersley (U.S. Pat.No. 4,813,997), which utilizes glycolic and/or lactic acid, and Young(U.S. Pat. Nos. 4,863,506 and 5,059,241) that disclose that d-lacticacid can promote increased plant growth, increased concentration ofchlorophyll, and increase the rate of root formation.

Gill (U.S. Pat. No. 5,047,078) utilized scale inhibiting compounds suchas those based on polymers of ethylenically unsaturated carboxylic acidsand/or maleic acid/anhydride monomers and/or phosphorous based chelatorssuch as dihydroxy ethylidene diphosphonic acid to make availablenutrients bound in the soil as insoluble salts and complexes resultingin increased growth and yields.

Kinnersley (U.S. Pat. Nos. 5,350,735 and 5,593,947) and Koskan (U.S.Pat. Nos. 5,783,523 and 5,814,582) teach using poly (organic) acids likepoly (amino acids) such as poly(aspartic) acid to enhance fertilizeruptake and promote plant growth.

Sanders (U.S. Pat. Nos. 6,753,395, 6,756,461, 6,818,039, and 8,043,995)demonstrate that man-made [P(OA)]s based on maleic, itaconic and/orcitraconic anhydrides can be utilized to enhance nutrient uptake byplants.

Sanders (U.S. Pat. Nos. 8,016,907 and 8,025,709) show the importance ofhaving a quick drying product that one can apply to the surface ofgranules for fertilizer. Sanders accomplish this by using 10-50% of avolatile alcohol such as methanol.

Many of these disclosures are now available in the marketplace. A 30%aqueous solution of sodium salt of a maleic-itaconic copolymer, (U.S.Pat. No. 6,515,090, Sanders), is marketed under the brand name Avail.Another polymer containing 40% sodium poly-lysine aqueous solution ismarketed as P-Max in the US market. A similar polymer, poly-aspartate,was also used for this purpose (U.S. Pat. No. 5,350,735 to 30Kinnersley). In the market, a composition that contains 30% aqueoussolution of sodium poly-aspartate is marketed as X10D (Flexible SolutionInternational). These products have been shown to increase the presenceof macronutrients and micronutrients in plant tissue.

However, all these products suffer from the same drawback. Mostfertilizers components tend to be solid granules and water soluble. Theabove-stated patents are almost exclusively based on aqueous solutionsand/or they contain >5% water. In many cases, the solid fertilizersapplied with a coating of an aqueous solution/dispersion can formagglomerations clogging field application equipment and making itdifficult to ensure an even distribution of fertilizer on fields. Ifthese granules of fertilizer have also been coated with amoisture-sensitive urease inhibitor like an alkyl thiophosphorictriamide, the presence of moisture from water based products will resultin degradation of these important urease inhibitors, negativelyimpacting/limiting their performance. Some innovations have to be soldas a costly, separate application product because of the presence ofwater. While other inventions teach that polymers are dried to formpowders and then blended into fertilizer compositions or by binding the[P(OA)] and or its salt to the fertilizer granules through liquidpolymers that act as a glue. However, this methodology usually requiresdrying to remove the binder's solvent to promote [P(OA)] adhesion to thegranule surface. Newer technologies utilize volatile organic solvents topromote quick drying, but this approach increases the VOC release andutilizes a low flash point alcohol such as methanol adding anunnecessary flammable hazard to the processing of fertilizer. But ofthese methods cannot utilize simple equipment such as a blender or mixerto apply a formulation comprising a layer of [P(OA)]s and/or their saltson the surface of solid fertilizer granules, soil and seeds safely,quickly, evenly, and economically.

For coating seeds with micronutrients, many technologies utilize aqueousdelivery systems that require an extra drying step. Because of thesensitivity of seeds to heat, most drying is accomplished either withvacuum extraction or through low temperature air flow drying. The dryingprocess is usually slow, can cause seeds to be dried below the moisturelevels required for good seed viability and adds cost to seedproduction. Various methods or variations of the above describedmechanism are listed in the patents below, which are incorporated byreference in their entireties.

Barclay (U.S. Pat. No. 5,994,265) reveals seed coating compositionincluding molybdenum (molybdenum trioxide), a sulfur-containingcomponent (gypsum) and an aqueous binder (polyvinyl alcohol) forimproving seed and seedling performance. Barclay also recognized theimportance of limiting the moisture content of the seeds/coating as tothe quality and viability of the seed.

Johnson (U.S. Pat. No. 7,001,869) teach how to produce a coated seedwith a treatment based on an aqueous formulation comprisingmacronutrients, micronutrients, an antimicrobial agent and otheradditives.

Obert (U.S. Pat. No. 6,557,298) teaches the utility of dry seed coatingsand that it helps to avoid the spoilage and premature germinationproblems associated with use of high water content. However, in practicethe application of such powders is accompanied by severe and undesirabledusting during processing and in application.

To address these problems, there is a need for a non-aqueous liquidformulation that can easily, safely, evenly and economically coatfertilizer granules and seeds without resulting in agglomeration duringblending and storage. These non-aqueous liquid formulations containcomponents that will liberate bound nutrients are safe for contact withhumans and animals, have low moisture, be environmentally friendly andbe applied as a coating to fertilizer and seed utilizing simple blendingequipment.

SUMMARY OF THE INVENTION

The present invention is comprised of one or more organic solvents thatcreate a non-aqueous organo solvent delivery system, (NOSDS), and one ormore poly(organic acids), [P(OA)]s, and/or their salts that results in astable, non-aqueous dispersion that can coat fertilizer granules andseeds easily, safely, evenly and economically.

In an embodiment, the present invention provides more flexibility forfertilizer manufacturers and farmers to produce fertilizers designed fora particular soil while including one or more of a NOSDS/[P(OA)]sformulation, nitrification inhibitors, urease inhibitors, pesticides,fungicides, herbicides, insecticides and micronutrients.

In an embodiment, the present invention relates to improving theefficiency of man-made and/or natural organic-based animal manurefertilizers by administration of formulations containing poly(organicacids), [P(OA)]s, and/or their salts dispersed in a Non-aqueous OrganicSolvent Delivery System (NOSDS). Utilizing a NOSDS allows for coatingall components in a fertilizer formulation including but not limited toUrea, Manure, mono-ammonium phosphate (MAP), di-ammonium phosphate(DAP), solid micronutrients such as lime, zinc chloride, etc.) with alayer of [P(OA)]s and/or their salts that liberates, in a plantavailable form, the micronutrient metals and macronutrients, that arebound as insoluble salts and complexes in the soil. The carboxylicgroups of a [P(OA)] that can exist within the [P(OA)] as carboxylicacids, carboxylic anhydrides and/or carboxylic imides, dispersed withinthe NOSDS, can be neutralized with one or more metals in the form ofelemental metals, metal oxides, metal hydroxides, metal alkylates andmetal carbonates and/or nitrogen containing compounds such as ammonia,ammonium hydroxide or organoamines to form a stable dispersion that cancontain completely complexed micronutrients and provide the vehicle forthe delivery of these nutrients to soils and/or as a coating to thesurfaces fertilizer granules and seeds. The metal or metal portions ofone of the reactant can further be defined for this invention as Na, K,Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni. Organoamine is one or more of thegroup consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, monoethanol amine, diethanol amine, triethanol amine, monoisopropyl amine,diisopropyl amine, triisopropyl amine, diethyl amine, diethylenetriamine, triethyl tetraamine, tetraethyl pentamine. It has also beenlearned that [P(OA)]s and/or their salts can be produced in situ in aNOSDS utilizing organic acids/esters monomers dispersed/suspended withinthe NOSDS, heated to a polymerization temperature with or withoutcatalyst and then neutralized/reacted with one or more macronutrientsand/or micronutrients. The liquid compositions of [P(OA)]s in a NOSDSand the methods to produce a [P(OA] within a NOSDS results in aflowable, low moisture liquid that can be readily mixed with liquidfertilizers or applied safely, quickly, evenly and economically on thesurface of solid fertilizer granules, soil and seeds.

A salt of a [P(OA)] is defined in this invention as thereaction/neutralization of one or more of the carboxylic groups of a[P(OA)] that can exist within the [P(OA)] as carboxylic acids,carboxylic anhydrides and/or carboxylic imides with one or more metalsin the form of elemental metals, metal oxides, metal hydroxides, metalalkylates and metal carbonates and/or with nitrogen containing compoundssuch as ammonia, ammonium hydroxide or organoamines resulting in astable dispersion of salts of [P(OA)] in a NOSDS. The metal or metalportions of one of the reactants can further be defined for thisinvention as Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, and/or Ni. Anorganoamine is one or more of the group consisting of mono C₁₋₆ amine,di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine, diethanol amine,triethanol amine, monoisopropyl amine, diisopropyl amine, triisopropylamine, diethyl amine, diethylene triamine, triethyl tetraamine, andtetraethyl pentamine.

In embodiments, the present invention also relates to improved solventformulations (NOSDS) for [P(OA)]s and/or their salts for application toman-made and/or natural organic based animal manure fertilizers. In avariation, [P(OA)]s may be solid chemical substances, which aredissolved in a suitable NOSDS to allow application at low levels in thefield. Additionally, non-aqueous solutions of [P(OA)]s may be desirablewhen they are to be incorporated as components of a granular mixedfertilizer, such that they can be deposited as a coating in a controlledand homogenous layer. In one embodiment, the [P(OA)]s can be produced insitu utilizing the starting organic acid/ester monomersdispersed/suspended within the NOSDS, heating the formulation to apolymerization temperature, with or without catalysts, and thenneutralizing/reacting the formulation with one or more macronutrientsand/or micronutrients. The composition can be utilized for coatingfertilizer granules and seeds and/or added to liquid fertilizers. In oneembodiment, this invention proposes formulations of NOSDS that comprisemixtures containing aprotic and/or protic solvents, which are moreenvironmentally friendly and are safe for manufacturers, transportersand others who work with/handle the compositions/formulations.

In one embodiment, improved liquid delivery formulations have beendeveloped that deliver effective levels of [P(OA)]s and/or their saltsthat can liberate nutrients bound in the soil as insoluble salts andcomplexes. It has been found that the liquid delivery formulations ofthe present invention provide a liquid vehicle, NOSDS, to deliver aneven, non-clumping layer of the desired [P(OA)]s and/or their salts tothe surfaces of fertilizer granules and/or seeds. These new liquiddelivery formulations for [P(OA)]s and/or their salts are non-aqueousorgano solvent delivery systems, NOSDSs, that improve the storage lifeof fertilizers containing urease inhibitors such as alkyl thiophosphorictriamides, acetohydroxamic acid and its derivatives, phosphodiamidatesrelative to those formulations containing greater than 1% water. Infact, because of the present invention, one can now combine [P(OA)]sand/or their salts, nitrification inhibitors, pesticides, fungicides,herbicides, insecticides and urease inhibitors in one product by eitherblending together the dispersions of each active ingredient or bycombining the pesticides, fungicides, herbicides, insecticides and thenitrification and urease inhibitors in the same improved solventformulation(s), NOSDS.

In embodiments, the present invention is compositions/formulations ofP(OA)]s and/or their salts in a NOSDS that:

-   -   Is environmentally safe;    -   Has flashpoints above 145° F.;    -   Is inherently rated safe for contact with humans and animals;    -   Provides stable dispersions of [P(OA)]s or their salts at levels        of 1-50% in the NOSDS at storage temperatures down to at least        10° C.;    -   Provides improved even application of a coating to fertilizer        granules and seeds while not causing clumping of the fertilizer        granules, premature seed germination and does not support of the        growth of mold and mildew on seeds;    -   Will not detrimentally impact the stability of alkyl        thiophosphoric triamides.

In one embodiment, it has been discovered that while various organicsolvents might meet some of the above criteria, the delivery system ofthe present invention can be optimized to provide a formulation with ahigh concentration of [P(OA)]s and/or their salts while maintaining alow chill point by combining two or more organic solvents as a NOSDS. Inone embodiment, one process for preparing the formulations of thepresent invention is to heat the combined solvents to temperatures60-100° C. and then charging the [P(OA)]s and/or their salts in acombined level of 10-60% of the total formula composition, which can bedissolved in the NOSDS with moderate agitation.

In one embodiment, the present invention relates to an effective solventcombination that comprises dimethyl sulfoxide (DMSO), which can be usedin combination with another liquid organo solvent that has a low chillpoint and good solvating properties. Besides the advantages listedabove, DMSO also has the advantage of potentially serving as a source ofthe important nutrient sulfur.

DETAILED DESCRIPTION

In an embodiment, the present invention is comprised of one or moreorganic solvents that create a non-aqueous organo solvent deliverysystem, (NOSDS), and one or more poly(organic acids), [P(OA)]s, and/ortheir salts in a stable, non-aqueous dispersion that can coat fertilizergranules and seeds easily, safely, evenly and economically.

A salt of a [P(OA)] is defined in this invention as the neutralizationof one or more of the carboxylic (carboxylate) groups of a [P(OA)] thatcan exist within the [P(OA)] as carboxylic acids, carboxylic anhydridesand/or carboxylic imides with one or more metals in the form ofelemental metals, metal oxides, metal hydroxides, metal alkylates andmetal carbonates and/or nitrogen containing compounds such as ammonia,ammonium hydroxide or organoamines resulting in a stable dispersion ofsalts of [P(OA)] in a NOSDS. The metal or metal portions of one of thereactant can further be defined for this invention as Na, K, Mg, Ca, Fe,Zn, Mn, Cu, Co, Mo, and/or Ni. [An organoamine is one or more of thegroup consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, monoethanol amine, diethanol amine, triethanol amine, monoisopropyl amine,diisopropyl amine, triisopropyl amine, diethyl amine, diethylenetriamine, triethyl tetraamine, and tetraethyl pentamine.

These delivery formulations not only provide a liquid vehicle to deliveran even, non-clumping coating of the desired [P(OA)]s and/or their saltsto the surfaces of fertilizer granules and/or seeds, but it has beendiscovered that formulations based on non-aqueous organo solventdelivery systems, NOSDS, do not negatively impact the storage life ofthe important urease inhibitors, such as alkyl thiophosphoric triamides(such as NBPT). Alkyl thiophosphoric triamides have been shown to beextremely effective urease inhibitors but if present in combination withan aqueously dispersed [P(OA)] and/or its salt, it will suffer fromdegradation upon storage if exposed to moisture present in aqueousdispersions. Thus, in one embodiment the present invention relates tocompositions that are substantially free of water.

In an embodiment, a stable dispersion of one or more [P(OA)]s and/ortheir salts in a non-aqueous organo solvent delivery system, NOSDS, cancontain and one or more of the following:

-   -   Urease inhibitor(s);    -   Nitrification inhibitor(s);    -   Pesticides, herbicides, fungicides and insecticides    -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker,    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents, micronutrients and/or flow modifiers such as        silica, zinc stearate, calcium stearate and the like.

In one embodiment, the improved solvent formulations, NOSDS, of thepresent invention meet one or more of the following criteria: They:

-   -   Are environmentally safe;    -   Have flashpoints above 145° F.;    -   Are inherently rated safe for contact with humans and animals;    -   Provide stable dispersions of [P(OA)]s or their salts at levels        of 1-50% within a NOSDS at storage temperatures down to at least        10° C.;    -   Provide improved even application of a coating to fertilizer        granules and seeds while not causing clumping of the fertilizer        granules, premature seed germination and does not support of the        growth of mold and mildew on seeds;    -   Will not detrimentally impact the stability of alkyl        thiophosphoric triamides.

In one embodiment, a stable non-aqueous, liquid formulation can beproduced that comprises a sodium polyaspartate (polymer weight=500 to10,000 or alternatively about 1000-7500 or alternatively 1500-5000 oralternatively about 1750-3000) and a NOSDS. In an embodiment, theformulations can be made by dissolving the sodium polyaspartate into aNOSDS comprised of one or more of the following a) one or more proticsolvents from the group consisting of

1) an alcohol from the family of C₁₋₁₀ alkanols, 2) polyols selectedfrom the group consisting of trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactose,and/or glycerin, 3) poly(C₁₋₁₀ alkylene) glycols, 4) alkylene glycolsselected from the group consisting of ethylene, 1,3 propylene glycol,1,2 propylene glycol, and/or butylene glycol, 5) isopropylidene glycerol6) alkylene glycol alkyl ethers selected from the group consisting oftripropylene glycol methyl ether, tripropylene glycol butyl ether,dipropylene glycol butyl ether and/or dipropylene glycol butyl ether, 7)ethyl, propyl, or butyl lactate, 8) an alkanolamine selected from thegroup consisting of ethanolamine, diethanolamine, dipropanolamine,methyl diethanolamine, monoisopropanolamine and/or triethanolamineand/or 9) glycerol carbonate.

b) and/or one or more aprotic solvents from the group consisting of

1) Dimethyl Sulfoxide and/or 2) dialkyl, diaryl, or alkylarylsulfoxide(s) having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₃ alkylenearyl group or R₁ and R₂ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₁ and R₂        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2.        3) alkylene carbonates selected from the group consisting of        ethylene carbonate, propylene carbonate and/or butylene        carbonate, 4) polyols capped with acetate or formate wherein the        polyol portion may be one or more of ethylene glycol, 1,3        propylene glycol, 1,2 propylene glycol, butylene glycol,        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol and sorbitan, glucose, fructose, galactose and/or        glycerin, 5) alkylene glycol alkyl ethers acetates selected from        the group consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and/or tripropylene        glycol butyl ether acetate and/or, 6) isophorone, 7)        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and/or        dimethyl glutarate, 8) dimethylacetamide, dimethylformamide,        dimethyl-2-imidazolidinone 9) hexamethylphosphoramide, 10)        1,2-dimethyloxethane, 2-methoxyethyl ether, 11)        cyclohexylpyrrolidone and/or 12) limonene.

Additionally, the liquid delivery formulations of the present inventionmay optionally contain one or more of the following:

-   -   Urease inhibitor(s);    -   Nitrification inhibitor(s);    -   Pesticides, herbicides, fungicides and insecticides    -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker,    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents, micronutrients and/or flow modifiers such as        silica, zinc stearate, calcium stearate and the like.

In an embodiment, the formulation may contain one or more [P(OA)]sand/or their salts comprised of the following monomers either ashomopolymers, copolymers and/or terpolymers at effective levels in theNOSDS wherein they may be present in an amount between about 5-50% ofthe total amount of the formulation. The [P(OA)]s may be

-   -   aspartic acid    -   C₁-C₆ partial or di-ester of aspartic acid    -   glutamic acid    -   C₁-C₆ partial or di-ester of glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid    -   C₁-C₆ partial or tri-ester of citric acid    -   acrylic acid    -   C₁-C₆ partial or full ester of acrylic acid    -   methacrylic acid    -   C₁-C₆ partial or full ester of methacrylic acid    -   maleic acid    -   C₁-C₆ partial or di-ester of maleic acid    -   itaconic acid    -   C₁-C₆ partial or di-ester of itaconic acid    -   citraconic acid    -   C₁-C₆ partial or di-ester of citraconic acid

In an embodiment, an 80/20 to 20/80 mix of dimethyl sulfoxide (DMSO) andethylene glycol is made and subsequently polyaspartic acid (or its saltor ester) is added with the polyaspartate being about 5-45% by weight ofthe total composition. In an embodiment, polyaspartate is added, underagitation, to the combined solvents that have been heated in a mixingvessel at a desired temperature of about 0° C. to 150° C., oralternatively at a temperature of about 10° C. to 120° C. oralternatively, at a temperature of about 20° C. to 100° C., oralternatively between about 50° C. and 100° C., and mixed until thepolyaspartate acid is completely dissolved. The heated mix vessel, inthis embodiment, may be jacketed and the temperature carefullycontrolled. In an embodiment, the mixing action should allow completemixing without too much aeration. In a variation, the heating may beaccomplished using hot water or low pressure steam to control any hotspots on walls of the vessel to prevent heat degradation. At this stage,the mixture can be cooled to about 35° C. and then the NBPT can be addedand agitated until completely dissolved. The mixture can be cooled to25° C. or below and one or more of the following may be added, ifdesired:

-   -   Urease inhibitor(s);    -   Nitrification inhibitor(s);    -   Pesticides, herbicides, fungicides and insecticides    -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker,    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents, micronutrients and/or flow modifiers such as        silica, zinc stearate, calcium stearate and the like.

It should be recognized that in the temperature ranges given above, theranges are set so as to allow adequate dissolution of the variouscompounds. The inventors recognize that should a compound be added thathas temperature stability issues, the additions may be under reducedpressure conditions so as to prevent temperature sensitive degradationsof the one or more compounds but at the same time allowing theirdissolution in the NOSDS.

In an embodiment, a polysuccinimide (PSI) powder (molecular weight of1000-10,000 may be added at a 5-50% level relative to a compositioncomprising ethylene glycol under agitation and at a temperature of60-80° C. The mixture is then heated to 100-180° C. and held until allparticles are dissolved. An alkaline or acid catalyst such as KOH orpTSA can be added to improve conversion from PSI to PolyaspartatePoly-EG ester. The batch is then cooled to 50-80° C. In an embodiment,KOH flakes are slowly charged, the temperature is held at 50-100° C. andmixed until all the KOH flakes are dissolved. In an embodiment, themixing action might include one or more of high shear devices such as acowles blade, a colloid mill, a rotor stator and/or a ball mill.

In an embodiment, a polysuccinimide (PSI) powder (molecular weight of3000-5000) may be added at a 5-50% level relative to a compositioncomprising ethylene glycol under agitation and at a temperature of60-80° C. The mixture is then heated to 100-180° C. and held until allparticles are dissolved and the PSI is converted to a PolyaspartatePoly-EG ester. An alkaline or acid catalyst such as KOH or pTSA can beadded to improve conversion from PSI to Polyaspartate Poly-EG ester. Thebatch is then cooled to 50-80° C. and the EG ester groups are partiallysaponified with enough of one or more metals in the form of elementalmetals, metal oxides, metal hydroxides, metal alkylates and metalcarbonates and/or with nitrogen containing compounds such as ammonia,ammonium hydroxide or organoamines to form a stable dispersion withinthe ethylene glycol. The metal or metal portions of one of the reactantcan further be defined for this invention as Na, K, Mg, Ca, Fe, Zn, Mn,Cu, Co, Mo, and/or Ni. An organoamine is one or more of the groupconsisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, monoethanol amine, diethanol amine, triethanol amine, monoisopropyl amine,diisopropyl amine, triisopropyl amine, diethyl amine, diethylenetriamine, triethyl tetraamine, and tetraethyl pentamine.

In an embodiment, the mixing action might include one or more of highshear devices such as a cowles blade, a colloid mill, a rotor statorand/or a ball mill.

In another embodiment, polyaspartate, ammonia salt, may be present at a10-50% level in a solution mix of DMSO and ethylene glycol at a ratio ofabout 80/20 to 20/80. In this embodiment, polyaspartate ammonia salt maybe added, under agitation to a NOSDS that is a blend of protic andprotic solvents that have been heated in a mixing vessel to a desiredtemperature of about 0° C. to 60° C., or alternatively, to a temperatureof about 10° C. to 50° C. and, alternatively, to a temperature of about20° C. to 40° C. and mixed until the polyaspartate, ammonia salt, iscompletely dissolved. Also in this embodiment, the heated mix vessel maybe jacketed and temperature controlled. In an embodiment, the mixingaction may allow complete mixing without too much aeration. In anembodiment the mixing action might include one or more of high sheardevices such as a cowles blade, a colloid mill, a rotor stator and/or aball mill. The heating may be accomplished using hot water and/or lowpressure steam to control any hot spots on the walls of the vessel,which can prevent heat degradation. At this stage, the mixture can becooled to about 25° C. or below and one or more of the followingadditives may be added, if desired:

-   -   Urease inhibitor(s);    -   Nitrification inhibitor(s);    -   Pesticides, herbicides, fungicides and insecticides    -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents, micronutrients and/or flow modifiers such as        silica, zinc stearate, and/or calcium stearate.

In an embodiment, polyaspartate and/or its acid may be added at a 5-50%level relative to a composition comprising ethylene glycol. In thisembodiment, polyaspartate acid may be added, under agitation, to thesolvent that has been heated in a mixing vessel at a temperature ofabout 0° C. to 60° C. and mixed until the polyaspartate is completelydissolved. In an embodiment, the heated mix vessel may be jacketed andthe temperature controlled. In a variation, the mixing action allowscomplete mixing without too much aeration. The heating can beaccomplished using hot water and/or low pressure steam to control anyhot spots on the walls of the vessel to prevent heat degradation. Atthis stage, the mixture may be cooled to 25° C. or below and one or moreof the following may be added, if desired:

-   -   Urease inhibitor(s);    -   Nitrification inhibitor(s);    -   Pesticides, herbicides, fungicides and insecticides    -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker,    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents, micronutrients and/or flow modifiers such as        silica, zinc stearate, and/or calcium stearate.

In an embodiment, polyaspartate ammonia salt may be incorporated at a5-50% level relative to the amount of ethylene glycol. In thisembodiment, polyaspartate ammonia may be added, under agitation, to theprotic solvent that has been heated in a mixing vessel at a temperatureof about 0° C. to 60° C. and mixed until the polyaspartate ammonia saltsare completely dissolved. The heated mix vessel may be jacketed and thetemperature controlled. In a variation, the mixing action allowscomplete mixing without too much aeration. The heating can beaccomplished using hot water or low pressure steam to control any hotspots on the walls of the vessel to prevent heat degradation. In avariation, the mixing action might include one or more of high sheardevices such as a cowles blade, a colloid mill, a rotor stator and/or aball mill. At this stage, the mixture may be cooled to 25° C. or belowand one or more of the following may be added, if desired:

-   -   Urease inhibitor(s);    -   Nitrification inhibitor(s);    -   Pesticides, herbicides, fungicides and insecticides    -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker,    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents, micronutrients and/or flow modifiers such as        silica, zinc stearate, and/or calcium stearate.

In an embodiment, polymaleic anhydride may be produced in a solvent suchas xylene utilizing an organic peroxide as a catalyst and using aprocess known to those of skill in the art. The resulting solvated poly(organic acid) can undergo solvent replacement by charging an aproticNOSDS comprised of one or more of 1) Dimethyl Sulfoxide and/or 2)dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₆ alkylenearyl group or R₁ and R₂ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₁ and R₂        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2.

3) alkylene carbonates selected from the group consisting of ethylenecarbonate, propylene carbonate and/or butylene carbonate, 4) polyolscapped with acetate or formate wherein the polyol portion may be one ormore of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,butylene glycol, trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactoseand/or glycerin, 5) alkylene glycol alkyl ethers acetates selected fromthe group consisting of dipropylene glycol methyl ether acetate,tripropylene glycol methyl ether acetate, and tripropylene glycol butylether acetate and/or, 6) isophorone, 7) dimethylsuccinate, dimethyladipate, diethyl glutarate, and/or dimethyl glutarate, 8)dimethylacetamide, dimethylformamide, dimethyl-2-imidazolidinone 9)hexamethylphosphoramide, 10) 1,2-dimethyloxethane, 2-methoxyethyl ether,11) cyclohexylpyrrolidone and/or 12) limonene.

One may then begin to strip the unwanted solvent out either bydifferential boiling points or by the use of a vacuum (such as by use ofa rotary evaporator) until the unwanted solvent is reduced to a levelthat is less than about 1%. The polymaleic anhydride can be neutralizedwithin the NOSDS to a desired pH with one or more metals in the form ofelemental metals, metal oxides, metal hydroxides, metal alkylates andmetal carbonates and/or with nitrogen containing compounds such asammonia, ammonium hydroxide or organoamines resulting in a stabledispersion of salts of [P(OA)] in a NOSDS. The metal or metal portionsof the reactants can further be defined as Na, K, Mg, Ca, Fe, Zn, Mn,Cu, Co, Mo and Ni or mixture thereof. Organoamine is one or more of thegroup consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, monoethanol amine, diethanol amine, triethanol amine, monoisopropyl amine,diisopropyl amine, triisopropyl amine, diethyl amine, diethylenetriamine, triethyl tetraamine, tetraethyl pentamine.

If water results from neutralization or from the addition of aqueoussolutions of these alkalis, the water can be removed by stripping (suchas by use of a rotary evaporator) through temperature or through lowertemperature/vacuum to ensure a low moisture formula. Other known meansof removing water can be used such as by use of molecular sieves or byaddition of a drying agent (such as Na₂SO₄ or MgSO₄) and subsequentfiltration.

In an embodiment, potassium polyaspartate can be incorporated in amountsthat are about 10-45% of a formulation mixture that also containsethylene and propylene glycol at ratios from about 80/20 to 20/80. In anembodiment, potassium polyaspartate may be added, under agitation, tothe combined solvents that have been heated in a mixing vessel at atemperature of about 0° C. to 150° C., or alternatively to a temperatureof about 20° C. to 130° C., or alternatively to a temperature of about40° C. to 120° C., or alternatively to a temperature of about 50° C. to100° C., and mixed until the potassium polyaspartate is completelydissolved. In an embodiment, the heated mix vessel may be jacketed andthe temperature carefully controlled. In a variation, the mixing actionallows complete mixing without too much aeration. Heating can beaccomplished using hot water or low pressure steam to control any hotspots on the walls of the vessel to prevent heat degradation to thepotassium polyaspartate. Alternatively, the mixing may be done atreduced pressure, the action can be performed in an inert atmosphere(such as but not limited to nitrogen, argon and/or carbon dioxide) tolimit thermal or oxidative degradation and/or the mixing action mightinclude one or more of high shear devices such as a cowles blade, acolloid mill, a rotor stator and/or a ball mill. At this stage (afterthe initial mixing), the mixture may be cooled to about 25° C. or belowand one or more of the following may be added, if desired:

-   -   Urease inhibitor(s);    -   Nitrification inhibitor(s);    -   Pesticides, herbicides, fungicides and insecticides    -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker,    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents, micronutrients and/or flow modifiers such as        silica, zinc stearate, and/or calcium stearate.

In another variation, the mixture of [P(OA)]s in NOSDS can be placedunder high shear agitation such as but not limited to an overheadagitator equipped with a cowles blade or a rotor stator mixer to assistin reducing viscosity of the mixture. In an embodiment, the presentinvention relates to making a stable non-aqueous dispersion of apolyaspartate salt in a NOSDS. In a variation a polysuccinimide isheated to 100-160° C. in the presence of an excess of a protic NOSDSresulting in the formation of a polyaspartate-ester dispersed in theprotic NOSDS which is subsequently saponified with one or more metals inthe form of elemental metals, metal oxides, metal hydroxides, metalalkylates and metal carbonates and/or with nitrogen containing compoundssuch as ammonia, ammonium hydroxide or organoamines resulting in astable dispersion of salts of [P(OA)] in a NOSDS. The metal or metalportions of the reactants can further be defined as Na, K, Mg, Ca, Fe,Zn, Mn, Cu, Co, Mo and Ni. An organoamine is one or more of the groupconsisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, monoethanol amine, diethanol amine, triethanol amine, monoisopropyl amine,diisopropyl amine, triisopropyl amine, diethyl amine, diethylenetriamine, triethyl tetraamine, and tetraethyl pentamine. In a variation,protic and/or aprotic solvent(s) can be added to the freed proticsolvent to give the composition the desired coating properties.

In an embodiment, the present invention relates to making the liquidcompositions that can be readily mixed with liquid fertilizers orapplied safely, quickly, evenly and economically on the surface of solidfertilizer granules, soil and seeds. In a variation, a polysuccinimideis heated to 100-160° C. in the presence of an excess of a proticsolvent resulting in the formation of a polyaspartate-ester dispersed inthe protic solvent which is subsequently reacted with oxides, hydroxides& carbonates of zinc, calcium, magnesium, iron, manganese, copper,cobalt, and/or nickel resulting in a stable dispersion of micronutrientsalts of polyaspartic acid ester in NOSDS. In a variation themicronutrient salts of polyaspartic acid ester in NOSDS can be fullyneutralized with one or more metals in the form of elemental metals,metal oxides, metal hydroxides, metal alkylates and metal carbonatesand/or with nitrogen containing compounds such as ammonia, ammoniumhydroxide or organoamines resulting in a stable dispersion of salts of[P(OA)] in a NOSDS. The metal or metal portions of the reactants canfurther be defined as Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo and Ni. Anorganoamine is one or more of the group consisting of mono C₁₋₆ amine,di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine, diethanol amine,triethanol amine, monoisopropyl amine, diisopropyl amine, triisopropylamine, diethyl amine, diethylene triamine, triethyl tetraamine, and/ortetraethyl pentamine. The NOSDS is free to become a component of thecomposition's organo solvent system. In a variation, the complexedmicronutrients have also been shown to have urease inhibitionperformance and thus can act both as a micronutrient and as a ureaseinhibitor.

In an embodiment, the present invention relates to making the liquidcompositions that can be readily mixed with liquid fertilizers orapplied safely, quickly, evenly and economically on the surface of solidfertilizer granules, soil and seeds. In a variation, a polysuccinimideis heated to 40-80° C. in the presence of an aprotic NOSDS and mixeduntil the polysuccinimide is completely dissolved. This dispersed[P(OA)]can be partially or fully neutralized with one or more metals inthe form of elemental metals, metal oxides, metal hydroxides, metalalkylates and metal carbonates and/or with nitrogen containing compoundssuch as ammonia, ammonium hydroxide or organoamines resulting in astable dispersion of salts of [P(OA)] in a NOSDS. The metal or metalportions of the reactants can further be defined as Na, K, Mg, Ca, Fe,Zn, Mn, Cu, Co, Mo, and Ni. An organoamine is one or more of the groupconsisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, monoethanol amine, diethanol amine, triethanol amine, monoisopropyl amine,diisopropyl amine, triisopropyl amine, diethyl amine, diethylenetriamine, triethyl tetraamine, and/or tetraethyl pentamine. The reactionvessel can be placed under vacuum to remove any residual water formed orintroduced.

In an embodiment, the present invention relates to making the liquidcompositions that can be readily mixed with liquid fertilizers orapplied safely, quickly, evenly and economically on the surface of solidfertilizer granules, soil and seeds. In a variation, a reactive monomeror a blend of reactive monomers such as but not limited to aspartic acidand/or glutamic acid is heated to 100-185° C. in the presence of a molarexcess of protic NOSDS resulting in the formation of a poly(organic-ester) which is subsequently saponified, freeing the NOSDS tobecome a component of the organo solvent system, with one or more metalsin the form of elemental metals, metal oxides, metal hydroxides, metalalkylates and metal carbonates and/or with nitrogen containing compoundssuch as ammonia, ammonium hydroxide or organoamines resulting in astable dispersion of salts of [P(OA)] in a NOSDS. The metal or metalportions of the reactants can further be defined as Na, K, Mg, Ca, Fe,Zn, Mn, Cu, Co, Mo and Ni. An organoamine is one or more of the groupconsisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, monoethanol amine, diethanol amine, triethanol amine, monoisopropyl amine,diisopropyl amine, triisopropyl amine, diethyl amine, diethylenetriamine, triethyl tetraamine, and/or tetraethyl pentamine. In avariation the molar ratio of the NOSDS to reactive monomer is 1.2 to 1.In another variation, the molar ratio of the NOSDS to reactive monomeris 6 to 1. In another variation the molar ratio of the NOSDS to reactivemonomer is 2 to 1. In another variation the molar ratio of the NOSDS toreactive monomer is 10 to 1. In one variation, the molar ratio may beany ratio between about 0.5 to 1 and 10 to 1. In a variation, the weightratio of the NOSDS to reactive monomer is 10% to 90%. In anothervariation, the weight ratio of the NOSDS to reactive monomer is 90% to10%.

In an embodiment, the present invention relates to making the liquidcompositions that can be readily mixed with liquid fertilizers orapplied safely, quickly, evenly and economically on the surface of solidfertilizer granules, soil and seeds. In a variation, a reactive monomeror a blend of reactive monomers such as but not limited to acrylic acid,maleic anhydride, maleic acid, citraconic anhydride itaconic anhydrideand/or itaconic acid is heated to 60-140° C. in the presence of a molarexcess protic NOSDS and with a free radical catalyst such as but notlimited to ammonium persulfate, benzoyl peroxide and/or di-tert butylperoxide resulting in the formation of a poly (organic-ester) which issubsequently saponified, freeing the NOSDS to become a component of theorgano solvent system, with one or more metals in the form of elementalmetals, metal oxides, metal hydroxides, metal alkylates and metalcarbonates and/or with nitrogen containing compounds such as ammonia,ammonium hydroxide or organoamines resulting in a stable dispersion ofsalts of [P(OA)] in a NOSDS. The metal or metal portions of thereactants can further be defined as Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co,Mo and Ni. An organoamine is one or more of the group consisting of monoC₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine, diethanolamine, triethanol amine, monoisopropyl amine, diisopropyl amine,triisopropyl amine, diethyl amine, diethylene triamine, triethyltetraamine, and/or tetraethyl pentamine.

In a variation, the molar ratio of the NOSDS to reactive monomer is 1.2to 1. In another variation, the molar ratio of the NOSDS to reactivemonomer is 6 to 1. In another variation the molar ratio of the NOSDS toreactive monomer is 2 to 1. In another variation, the molar ratio of theNOSDS to reactive monomer is 10 to 1. In one variation, the molar ratiomay be any ratio between about 0.5 to 1 and 10 to 1.

In a variation, the weight ratio of the NOSDS to reactive monomer is 10%to 90%. In another variation, the weight ratio of the NOSDS to reactivemonomer is 90% to 10%.

In an embodiment, polyacrylic acid may be produced in a solvent such asmethyl ethyl ketone using a peroxide catalyst and a process known tothose experienced in the art. The resulting solvated poly (organic acid)can undergo solvent replacement by charging an aprotic NOSDS comprisedof one or more of 1) Dimethyl Sulfoxide and/or 2) dialkyl, diaryl, oralkylaryl sulfoxide(s) having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₆ alkylenearyl group or R₁ and R₂ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₁ and R₂        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2.        and/or 3) alkylene carbonates such as ethylene carbonate,        propylene carbonate and/or butylene carbonate and/or 4) polyols        capped with acetate or formate wherein the polyol portion may be        one or more of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol, propane        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and/or glycerin 5) alkylene glycol        alkyl ethers acetates such as tripropylene glycol methyl ether        acetate, tripropylene glycol butyl ether acetate and/or 6)        isophorone 7) dimethylsuccinate, dimethyl adipate, diethyl        glutarate, and/or dimethyl glutarate, 8) dimethylacetamide,        dimethylformamide, dimethyl-2-imidazolidinone 9)        hexamethylphosphoramide, 10) 1,2-dimethyloxethane,        2-methoxyethyl ether, 11) cyclohexylpyrrolidone, and/or 12)        limonene.

Subsequently, one can then begin to strip the unwanted solvent outeither by differential boiling points or by the use of vacuum until theunwanted solvent is reduced to a level that is less than about 1%. Thepolyacrylic acid can be neutralized in the new NOSDS to a desired pHwith one or more metals in the form of elemental metals, metal oxides,metal hydroxides, metal alkylates and metal carbonates and/or withnitrogen containing compounds such as ammonia, ammonium hydroxide ororganoamines resulting in a stable dispersion of salts of [P(OA)] in aNOSDS. The metal or metal portions of the reactants can further bedefined as Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo and Ni. A organoamineis one or more of the group consisting of mono C₁₋₆ amine, di C₁₋₆amine, tri C₁₋₆ amine, mono ethanol amine, diethanol amine, triethanolamine, monoisopropyl amine, diisopropyl amine, triisopropyl amine,diethyl amine, diethylene triamine, triethyl tetraamine, and/ortetraethyl pentamine. If water resulting from neutralization or from theaddition of aqueous solutions of these alkalis is present, the water canbe removed by stripping (such as by use of a rotary evaporator) throughtemperature or through lower temperature/vacuum to insure a low moistureformula. Alternatively, molecular sieves or drying agents and filtrationmay be used.

In an embodiment, one or more additional urease inhibitors, one or moreadditional [P(OA)]s and/or one or more additional nitrificationinhibitors may be added to formulations of the present invention. In anembodiment, the additional urease inhibitor, [P(OA)]s and/ornitrification inhibitors may be dissolved in the mixture. In anembodiment, useful mixtures may be prepared either by dilution ormixture with liquid fertilizers.

Examples of the present formulation include adding the liquid inventionto an aqueous mixture of urea and ammonium nitrate (UAN) or coating withthe liquid invention by contacting the mixture with solid fertilizerscomponents such as formulation including but not limited to Urea,Manure, mono-ammonium phosphate (MAP), di-ammonium phosphate (DAP),solid micronutrients such as lime, zinc chloride, etc). In anembodiment, coated granular fertilizer can be prepared by using anycommercially available equipment in which granular product can be mixedor sprayed with the liquid invention. A flow aid, silicas or surfactantssuch as soap or nonionic surfactants may be added prior to addition ofthe liquid for improved dispersability.

In an embodiment, the resulting coated fertilizer can be applied to soilin either a liquid and/or a granular form to provide improved nutrientretention in the soil for uptake for plant life.

In an embodiment, the active ingredients are comprised of one or morenitrification inhibitors, one or more urease inhibitors, one or morepesticides, one or more fungicides, one or more herbicides and/or one ormore insecticides dispersed within a stable liquid formulation comprisedof a one or more polyaspartic acid and/or its salts and a NOSDS (such asthe ones described herein).

In an embodiment, the composition may comprise one or more ofsurfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, pesticides, fungicides, herbicides, insecticides and/orflow modifiers.

In an embodiment, the composition is substantially free of water.

In an embodiment, the present invention relates to fertilizer additives.In one embodiment, the fertilizer additive comprises one or morenitrification inhibitors, one or more pesticides, one or morefungicides, one or more herbicides, one or more insecticides and one ormore urease inhibitors within a stable liquid formulation comprised of aone or more [P(OA)]s and/or their salts and a NOSDS.

In an embodiment, the present invention relates to fertilizer or seedadditives that comprises one or more of the following:

-   -   a) one or more fungicides such as but not limited to        azoxystrobin, bacillus lichenformis, boscalid, captan,        chloroneb, chlorothalonil, ethazole (etridiazole), fenarimol,        fludioxonil, flutolanil, fosetyl-aluminum, iprodione, mancozeb,        mefenoxam, myclobutanil, potassium phosphite, polyoxin D,        propamocarb, propiconazole, pyraclostrobin, tebuconazole,        thiophanate-methyl, thiram, triadimefon, trifloxystrobin,        vinclozolin;    -   b) one or more herbicides such as but not limited to 2,4-D,        2,4-DB, acetochlor, acifluorfen, alachlor, ametryn, atrazine,        aminopyralid, benefin, bensulfuron, bensulide, bentazon,        bromacil, bromoxynil, butylate, carfentrazone, chlorimuron,        chlorsulfuron, clethodim, clomazone, clopyralid, cloransulam,        cycloate, DCPA, desmedipham, dicamba, dichlobenil, diclofop,        diclosulam, diflufenzopyr, dimethenamid, diquat, diuron, DSMA,        endothall, EPTC, ethalfluralin, ethofumesate, fenoxaprop,        fluazifop-P, flucarbazone, flufenacet, flumetsulam, flumiclorac,        flumioxazin, fluometuron, fluroxypyr, fomesafen, foramsulfuron,        glufosinate, glyphosate, halosulfuron, hexazinone,        imazamethabenz, imazamox, imazapic, imazaquin, imazethapyr,        isoxaben, isoxaflutole, lactofen, linuron, MCPA, MCPB,        mesotrione, metolachlor-s, metribuzin, metsulfuron, molinate,        MSMA, napropamide, naptalam, nicosulfuron, norflurazon,        oryzalin, oxadiazon, oxyfluorfen, paraquat, pelargonic acid,        pendimethalin, phenmedipham, picloram, primisulfuron,        prodiamine, prometryn, pronamide, propanil, prosulfumon,        pyrazon, pyrithiobac, quinclorac, quizalofop, rimsulfuron,        sethoxydim, siduron, simazine, sulfentrazone, sulfometuron,        sulfosulfuron, tebuthiuron, terbacil, thiazopyr, thifensulfuron,        thiobencarb, tralkoxydim, triallate, triasulfuron, tribenuron,        triclopyr, trifluralin, triflusulfuron;    -   c) and/or one or more insecticides such as but not limited to        bifenthrin, cypermethrin, permethrin, piperonyl butoxide,        lambda-cyhalothrin, (s)-methoprene, deltamethrin, permethrin,        esfenvalerate, pyriproxyfen, fipronil, etofenprox, cyphenothrin,        carbofuran, chlorpoyrifos, disulfoton, fenvalerate, ethoprop,        fonofos, malathion, permethrin, phorate, tefluthrin, terbufos,        trimcthacarb, allicin, anabasine, azadirachtin, carvacrol,        d-limonenc, matrine, nicotine, nornicotine, oxymatrine,        pyrethrins, cinerins, jasmolin, quassia, rhodojaponin, rotenone,        ryania, sabadilla, sanguinarine, triptolide, carbamate        insecticides, benzofuranyl methylcarbamate insecticides,        dimethylcarbamate insecticides, oxime carbamate insecticides,        phenyl methylcarbamate insecticides, dinosam, DNOC, fluorine        insecticides, formamidine insecticides, amitraz, chlordimeform,        formetanate, formparanate, medimeform, semiamitraz;        within a stable liquid formulation comprised of a one or more        [P(OA)]s and/or their salts and a NOSDS. In a variation, one or        more nitrification inhibitors, one or more urease inhibitors can        be added to the stable liquid formulation.

In an embodiment, the present invention relates to seed additives. Inone embodiment, the seed additive comprises one or more nitrificationinhibitors, pesticides, fungicides, herbicides, insecticides and one ormore urease inhibitors within a stable liquid formulation comprised of aone or more [P(OA)]s and/or their salts and a NOSDS

In an embodiment, the present invention relates to making compositionsand fertilizer and/or seed additives. In one embodiment, the presentinvention relates to a method of making a composition to be added to afertilizer and/or seeds, wherein the method comprises:

heating a mixture comprising one or more [P(OA)] and/or its salt in aNOSDS;

cooling the mixture to a temperature that optionally allows addition ofone or more of surfactants, buffers, fragrance/odor masking agents,colorants, micro-nutrients, pesticides, fungicides, herbicides,insecticides and/or flow modifiers.

In one variation of the method, the method comprises further adding thecomposition to a fertilizer and/or seeds.

In an embodiment, a stable liquid formulation composition comprising oneor more [P(OA)]s and/or their salts in a protic NOSDS wherein the proticNOSDS is comprised of one or more of 1) an alcohol from the family ofC₁₋₁₀ alkanols, 2) polyols selected from the group consisting oftrimethylol propane, trimethylol ethane, pentaerythritol, sorbitol andsorbitan, glucose, fructose, galactose, and glycerin, 3) poly(C₁₋₁₀alkylene) glycols, 4) alkylene glycols selected from the groupconsisting of ethylene, 1,3 propylene glycol, 1,2 propylene glycol, andbutylene glycol, 5) isopropylidene glycerol 6) alkylene glycol alkylethers selected from the group consisting of tripropylene glycol methylether, tripropylene glycol butyl ether, dipropylene glycol butyl etherand dipropylene glycol butyl ether, 7) ethyl, propyl, or butyl lactate,8) an alkanolamine selected from the group consisting of ethanolamine,diethanolamine, dipropanolamine, methyl diethanolamine,monoisopropanolamine and triethanolamine and/or 9) glycerol carbonate.

In an embodiment, the formulation may contain one or more [P(OA)]sand/or their salts comprised of the following monomers either ashomopolymers, copolymers and/or terpolymers at effective levels in theNOSDS wherein they may be present in an amount between about 5-50% ofthe total amount:

-   -   aspartic acid    -   C₁-C₆ partial or di-ester of aspartic acid    -   glutamic acid    -   C₁-C₆ partial or di-ester of glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid    -   C₁-C₆ partial or tri-ester of citric acid    -   acrylic acid    -   C₁-C₆ partial or full ester of acrylic acid    -   methacrylic acid    -   C₁-C₆ partial or full ester of methacrylic acid    -   maleic acid    -   C₁-C₆ partial or di-ester of maleic acid    -   itaconic acid    -   C₁-C₆ partial or di-ester of itaconic acid    -   citraconic acid, and/or    -   C₁-C₆ partial or di-ester of citraconic acid

In a variation, the composition may contain a protic NOSDS from thegroup that is comprised of one or more of ethylene glycol, propyleneglycol, butylene glycol, glycerin, tripropylene glycol and/or theirmethyl ethers.

In a variation, the one or more protic NOSDS comprise between about90/10 to 10/90 of the composition.

In a variation, the one or more [P(OA)] and or their salts is potassiumaspartate in a formulation wherein potassium aspartate is present in anamount that is between about 10-45% of a total formulation amount andthe formulation also contains a mixture of ethylene glycol and propyleneglycol in ratios that are between about 20/80 to 80/20.

In an embodiment, the composition may further comprise one or more ofsurfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, dispersed urease inhibitor(s), dispersed nitrificationinhibitor(s), dispersed pesticides, dispersed fungicides, dispersedherbicides, dispersed insecticides and/or flow modifiers.

In a variation, the composition is substantially free of water.

In an embodiment, a composition comprising a stable dispersion of one ormore [P(OA)]s and/or their salts in a NOSDS comprised of

a) one or more protic solvents selected from the group consisting of 1)an alcohol from the family of C₁₋₁₀ alkanols, 2) polyols selected fromthe group consisting of trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactose,and/or glycerin, 3) poly(C₁₋₁₀ alkylene) glycols, 4) alkylene glycolsselected from the group consisting of ethylene, 1,3 propylene glycol,1,2 propylene glycol, and/or butylene glycol, 5) isopropylidene glycerol6) alkylene glycol alkyl ethers selected from the group consisting oftripropylene glycol methyl ether, tripropylene glycol butyl ether,dipropylene glycol butyl ether and/or dipropylene glycol butyl ether, 7)ethyl, propyl, or butyl lactate, 8) an alkanolamine selected from thegroup consisting of ethanolamine, diethanolamine, dipropanolamine,methyl diethanolamine, monoisopropanolamine and/or triethanolamineand/or 9) glycerol carbonate.

b) and/or one or more aprotic solvent from the group consisting of 1)Dimethyl Sulfoxide and/or 2) dialkyl, diaryl, or alkylaryl sulfoxide(s)having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₆ alkylenearyl group or R₁ and R₂ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₁ and R₂        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2.

3) alkylene carbonates selected from the group consisting of ethylenecarbonate, propylene carbonate and/or butylene carbonate, 4) polyolscapped with acetate or formate wherein the polyol portion may be one ormore of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,butylene glycol, trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactoseand/or glycerin, 5) alkylene glycol alkyl ethers acetates selected fromthe group consisting of dipropylene glycol methyl ether acetate,tripropylene glycol methyl ether acetate, and/or tripropylene glycolbutyl ether acetate and/or, 6) isophorone, 7) dimethylsuccinate,dimethyl adipate, diethyl glutarate, and/or dimethyl glutarate, 8)dimethylacetamide, dimethylformamide, dimethyl-2-imidazolidinone 9)hexamethylphosphoramide, 10) 1,2-dimethyloxethane, 2-methoxyethyl ether,11) cyclohexylpyrrolidone and/or 12) limonene.

In a variation, the composition may contain one or more [P(OA)]s and/ortheir salts comprised of the following monomers either as homopolymers,copolymers and/or terpolymers at effective levels in the NOSDS whereinthey may be present in an amount between about 5-50% of the totalamount:

-   -   aspartic acid    -   C₁-C₆ partial or di-ester of aspartic acid    -   glutamic acid    -   C₁-C₆ partial or di-ester of glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid    -   C₁-C₆ partial or tri-ester of citric acid    -   acrylic acid    -   C₁-C₆ partial or full ester of acrylic acid    -   methacrylic acid    -   C₁-C₆ partial or full ester of methacrylic acid    -   maleic acid    -   C₁-C₆ partial or di-ester of maleic acid    -   itaconic acid    -   C₁-C₆ partial or di-ester of itaconic acid    -   citraconic acid    -   C₁-C₆ partial or di-ester of citraconic acid

In an embodiment, the composition may contain a protic NOSDS whichcomprises one or more of the following: ethylene glycol, propyleneglycol, butylene glycol, glycerin, tripropylene glycol methyl ether

In a variation, an aprotic NOSDS which comprises one or more of thefollowing: dimethyl sulfoxide, propylene carbonate, dimethylsuccinate,diethyl glutarate, or dimethyl glutarate.

In a variation, the ratio of protic NOSDS to aprotic NOSDS is betweenabout 90/10 to 10/90% and a total of the solvating system is betweenabout 10 to 90% of a final composition.

In a variation, the one or more [P(OA)]s and/or their salts comprisesodium aspartate in a formulation wherein sodium aspartate is present inan amount that is between about 10-45% of a total formulation amount andthe formulation also contains a) ethylene glycol and/or propylene glycoland b) propylene carbonate in a ratio that is between about 20/80 to80/20.

In a variation, the composition is substantially free of water.

In an embodiment, the present invention relates to a stable liquidfertilizer and/or seed additive, which comprises one or more [P(OA)]sand/or their salts in a NOSDS comprised of one or more of a) proticsolvents from the group consisting of 1) an alcohol from the family ofC₁₋₁₀ alkanols, 2) polyols selected from the group consisting oftrimethylol propane, trimethylol ethane, pentaerythritol, sorbitol andsorbitan, glucose, fructose, galactose, and/or glycerin, 3) poly(C₁₋₁₀alkylene) glycols, 4) alkylene glycols selected from the groupconsisting of ethylene, 1,3 propylene glycol, 1,2 propylene glycol,and/or butylene glycol, 5) isopropylidene glycerol 6) alkylene glycolalkyl ethers selected from the group consisting of tripropylene glycolmethyl ether, tripropylene glycol butyl ether, dipropylene glycol butylether and/or dipropylene glycol butyl ether, 7) ethyl, propyl, or butyllactate, 8) an alkanolamine selected from the group consisting ofethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine,monoisopropanolamine and/or triethanolamine and/or 9) glycerolcarbonate.

b) and/or one or more aprotic solvents from the group consisting of 1)Dimethyl Sulfoxide and/or 2) dialkyl, diaryl, or alkylaryl sulfoxide(s)having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₆ alkylenearyl group or R₁ and R₂ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₁ and R₂        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2.

3) alkylene carbonates selected from the group consisting of ethylenecarbonate, propylene carbonate and/or butylene carbonate, 4) polyolscapped with acetate or formate wherein the polyol portion may be one ormore of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,butylene glycol, trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactoseand/or glycerin, 5) alkylene glycol alkyl ethers acetates selected fromthe group consisting of dipropylene glycol methyl ether acetate,tripropylene glycol methyl ether acetate, and/or tripropylene glycolbutyl ether acetate and/or, 6) isophorone, 7) dimethylsuccinate,dimethyl adipate, diethyl glutarate, and/or dimethyl glutarate, 8)dimethylacetamide, dimethylformamide, dimethyl-2-imidazolidinone 9)hexamethylphosphoramide, 10) 1,2-dimethyloxethane, 2-methoxyethyl ether,11) cyclohexylpyrrolidone and/or 12) limonene.

In a variation, the fertilizer and/or seed additive may contain one ormore [P(OA)]s and/or their salts comprised of the following monomers ashomopolymers, copolymers and/or terpolymers at effective levels in theNOSDS wherein they may be present in an amount between about 5-50% ofthe total amount:

-   -   aspartic acid    -   C₁-C₆ partial or di-ester of aspartic acid    -   glutamic acid    -   C₁-C₆ partial or di-ester of glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid    -   C₁-C₆ partial or tri-ester of citric acid    -   acrylic acid    -   C₁-C₆ partial or full ester of acrylic acid    -   methacrylic acid    -   C₁-C₆ partial or full ester of methacrylic acid    -   maleic acid    -   C₁-C₆ partial or di-ester of maleic acid    -   itaconic acid    -   C₁-C₆ partial or di-ester of itaconic acid    -   citraconic acid    -   C₁-C₆ partial or di-ester of citraconic acid

In a variation, the fertilizer additive may further comprise one or morepesticides, herbicides, fungicides and/or insecticide.

In a variation, the fertilizer additive may further comprising one ormore nitrification inhibitors wherein the one or more nitrificationinhibitors is selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide, thiourea,1-mercapto-1,2,4-triazole, 3,4-dimethylpyrazole phosphate, and2-amino-4-chloro-6-methylpyrimidine.

In an embodiment, the fertilizer additive may further comprise one ormore urease inhibitors wherein the one or more urease inhibitors isselected from the group consisting of phosphoric triamides,thiophosphoric triamides and alkylated thiophosphoric triamides, whereinthe alkylated thiophosphoric triamides has one or more alkyl groups thatindependently contain between 1 and 6 carbon atoms.

In a variation, the fertilizer and/or seed additive may comprise one ormore nitrification inhibitors wherein the one or more nitrificationinhibitors comprise dicyandiamide, the one or more [P(OA)]s comprisepolyaspartic acid and the one or more urease inhibitors comprisephosphoric triamides. Alternatively, the one or more urease inhibitorsmay comprise a phosphoramide.

In an embodiment, the present invention relates to a method of making acomposition to be added as a coating to the surface of a fertilizergranules and/or seeds comprising:

heating a mixture comprises one or more [P(OA)]s and/or their salts in aNOSDS comprised of a) one or more protic solvents from the groupconsisting of 1) an alcohol from the family of C₁₋₁₀ alkanols, 2)polyols selected from the group consisting of trimethylol propane,trimethylol ethane, pentaerythritol, sorbitol and sorbitan, glucose,fructose, galactose, and/or glycerin, 3) poly(C₁₋₁₀ alkylene) glycols,4) alkylene glycols selected from the group consisting of ethylene, 1,3propylene glycol, 1,2 propylene glycol, and/or butylene glycol, 5)isopropylidene glycerol 6) alkylene glycol alkyl ethers selected fromthe group consisting of tripropylene glycol methyl ether, tripropyleneglycol butyl ether, dipropylene glycol butyl ether and/or dipropyleneglycol butyl ether, 7) ethyl, propyl, or butyl lactate, 8) analkanolamine selected from the group consisting of ethanolamine,diethanolamine, dipropanolamine, methyl diethanolamine,monoisopropanolamine and/or triethanolamine and/or 9) glycerolcarbonate.

b) and/or one or more aprotic solvents from the group consisting of 1)Dimethyl Sulfoxide and/or 2) dialkyl, diaryl, or alkylaryl sulfoxide(s)having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₆ alkylenearyl group or R₁ and R₂ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₁ and R₂        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2.

3) alkylene carbonates selected from the group consisting of ethylenecarbonate, propylene carbonate and/or butylene carbonate, 4) polyolscapped with acetate or formate wherein the polyol portion may be one ormore of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,butylene glycol, trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactoseand/or glycerin, 5) alkylene glycol alkyl ethers acetates selected fromthe group consisting of dipropylene glycol methyl ether acetate,tripropylene glycol methyl ether acetate, and/or tripropylene glycolbutyl ether acetate and/or, 6) isophorone, 7) dimethylsuccinate,dimethyl adipate, diethyl glutarate, and/or dimethyl glutarate, 8)dimethylacetamide, dimethylformamide, dimethyl-2-imidazolidinone 9)hexamethylphosphoramide, 10) 1,2-dimethyloxethane, 2-methoxyethylether, 1) cyclohexylpyrrolidone and/or 12) limonene;

and cooling the mixture to a temperature that optionally allows additionof one or more of surfactants, buffers, fragrance/odor masking agents,colorants, micro-nutrients, dispersed urease inhibitor(s), dispersednitrification inhibitor(s), pesticide(s), herbicide(s) fungicide(s)and/or flow modifiers.

In an embodiment, the method may further comprise adding the compositionto a fertilizer and/or seed.

In a variation, the fertilizer and/or seed additive may contain one ormore [P(OA)]s and/or their salts comprised of the following monomers ashomopolymers, copolymers and/or terpolymers at effective levels in theNOSDS wherein they may be present in an amount between about 5-50% ofthe total:

-   -   aspartic acid    -   C₁-C₆ partial or di-ester of aspartic acid    -   glutamic acid    -   C₁-C₆ partial or di-ester of glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid    -   C₁-C₆ partial or tri-ester of citric acid    -   acrylic acid    -   C₁-C₆ partial or full ester of acrylic acid    -   methacrylic acid    -   C₁-C₆ partial or full ester of methacrylic acid    -   maleic acid    -   C₁-C₆ partial or di-ester of maleic acid    -   itaconic acid    -   C₁-C₆ partial or di-ester of itaconic acid    -   citraconic acid and/or    -   C₁-C₆ partial or di-ester of citraconic acid        wherein the one or more [P(OA)]s are present at a level that is        between about 5-50% of a total composition.

In a variation, the method may use dispersed nitrification inhibitorsthat is/are one or more members selected from the group consisting of2-chloro-6-trichloromethylpyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide, thiourea,1-mercapto-1,2,4-triazole, 2-amino-4-chloro-6-methylpyrimidine, and3,4-dimethylpyrazole phosphate.

In an embodiment, the method may comprise one or more dispersed ureaseinhibitors wherein they are one or more members selected from the groupconsisting of phosphoric triamides, thiophosphoric triamides andalkylated thiophosphoric triamides, wherein the alkylated thiophosphorictriamides has one or more alkyl groups that independently containbetween 1 and 6 carbon atoms.

In a variation, the method may comprise a dispersed nitrificationinhibitor and a dispersed urease inhibitor wherein the dispersednitrification inhibitor comprises dicyandiamide and the dispersed ureaseinhibitor comprises phosphoric triamides. Alternatively, the dispersedurease inhibitor may comprise a phosphoramide.

In a variation, the method may use a composition that is substantiallyfree of water. Substantially free of water means less than about 1%water.

In a variation, the present invention relates to a compositioncomprising one or more Poly (organic acids), [P(OA)]s, and/or theirsalt(s) and one or more of a Non-aqueous Organo Solvent Delivery System(NOSDS), wherein said composition is a stable dispersion ideally suitedto coat man-made and/or natural fertilizer components and/or seedswherein the [P(OA)]s are homopolymers, copolymers and/or terpolymersthat are comprised of one or more of the following monomers:

aspartic acid, glutamic acid, maleic acid, itaconic acid, citraconicacid, citric acid, acrylic acid, methacrylic acid, itaconic acid, andcitraconic acid, their C₁₋₆ esters, anhydrides, and imides, or theirsalts;

and wherein the NOSDS is comprised of one or more of;

a) protic solvents selected from the group consisting of:

a C1-10 alcohol, 2) one or more polyols selected from the groupconsisting of trimethylol propane, trimethylol ethane, pentaerythritol,sorbitol and sorbitan, glucose, fructose, galactose, and glycerin, 3)poly(C1-10 alkylene) glycols, 4) alkylene glycols selected from thegroup consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propyleneglycol, and butylene glycol, 5) isopropylidene glycerol 6) alkyleneglycol alkyl ethers selected from the group consisting of tripropyleneglycol methyl ether, tripropylene glycol butyl ether, dipropylene glycolbutyl ether and dipropylene glycol butyl ether, 7) ethyl, propyl, orbutyl lactate, 8) an alkanolamine selected from the group consisting ofethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine,monoisopropanolamine and triethanolamine and 9) glycerol carbonate

and/or

b) one or more aprotic solvents comprising one or more of 1) dimethylsulfoxide 2) a dialkyl sulfoxide, diaryl sulfoxide, or an alkylarylsulfoxide having the formula:

R₁S(O)_(x)R₂

wherein R₁ and R₂ are each independently a C₁₋₆ alkyl group, an arylgroup, or

C₁₋₃alkylenearyl group, or R₁ and R₂ with the sulfur to which they areattached form a 4 to 7 membered ring wherein R₁ and R₂ together are aC₁₋₆ alkylene group which optionally contains one or more atoms selectedfrom the group consisting of O, S, Se, Te, N, and P in the ring and x is1 or 2 or

3) an alkylene carbonate selected from the group consisting of ethylenecarbonate, propylene carbonate and butylene carbonate, 4) a polyolcapped with acetate or formate wherein the polyol portion is one or moreof ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butyleneglycol, trimethylol propane, trimethylol ethane, pentaerythritol,sorbitol, sorbitan, glucose, fructose, galactose or glycerin, 5) analkylene glycol alkyl ether acetates selected from the group consistingof dipropylene glycol methyl ether acetate, tripropylene glycol methylether acetate, and tripropylene glycol butyl ether acetate, 6)isophorone, 7) dimethylsuccinate, dimethyl adipate, diethyl glutarate,and/or dimethyl glutarate, 8) dimethylacetamide, dimethylformamide,dimethyl-2-imidazolidinone 9) hexamethylphosphoramide, 10)1,2-dimethyloxyethane, 2-methoxyethyl ether, 11) cyclohexylpyrrolidoneand/or 12) limonene.

In an embodiment, the salts are derived from metals, metal hydroxides,metal alkylates, metal carbonates, ammonia, ammonium hydroxide, ororganoamines.

In an embodiment, wherein the metals in the metals, metal hydroxides,metal alkylates, or metal carbonates comprise one or more of Na, K, MgCa, Fe, Zn, Mn, Cu, Co, Mo or Ni.

In a variation, the organoamines comprise one or more of mono C₁₋₆amine, di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine, diethanolamine, triethanol amine, monoisopropanol amine, diisopropanol amine,triisopropanol amine, ethylene diamine diethylene triamine, triethylenetetraamine, or tetraethylene pentamine.

In a variation, the composition comprises one or more protic solvents orone or more aprotic solvents.

In an embodiment, the composition:

-   -   i Is Environmentally safe;    -   ii Has flashpoints above 145° F.;    -   iii Is inherently rated safe for contact with humans and        animals;    -   iv Provides stable dispersions of [P(OA)]s or their salts at        levels of 1-50% in the NOSDS at storage temperatures down to at        least 10° C.;    -   v Provides improved, even application of a coating to fertilizer        granules and seeds while not causing clumping of the fertilizer        granules, premature seed germination and does not support the        growth of mold and mildew on seeds; and    -   vi Will not detrimentally impact the stability of alkyl        thiophosphoric triamides.

In a variation, the NOSDS comprises one or more protic solvents whereinthe [P(OA)]s to the one or more protic solvent ratio is between about90/10 to 10/90.

In a variation, the one or more [P(OA)]s comprises a potassium salt of apolyaspartate wherein the potassium salt of the polyaspartate is presentin an amount that is between about 10-45% of a total composition amountand the NOSDS of the formulation is ethylene glycol.

In an embodiment, the composition may further comprise one or more ofsurfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, dispersed urease inhibitor(s), dispersed nitrificationinhibitor(s), pesticide(s), fungicides(s), herbicide(s), insecticide(s)or flow modifiers.

In an embodiment, the composition is substantially free of water.

In an embodiment, the present invention relates to a process forproducing the composition, wherein said process comprises procuring oneor more of the following monomers:

-   -   aspartic acid, glutamic acid, maleic acid, itaconic acid,        citraconic acid, citric acid, acrylic acid, methacrylic acid,        itaconic acid, and citraconic acid, their C₁₋₆ esters,        anhydrides, and imides, or their salts; and dispersing said one        or more monomers into an aprotic solvent to create a dispersion        wherein said aprotic solvent comprises one or more of 1)        dimethyl sulfoxide 2) dialkyl, diaryl, or alkylaryl sulfoxide(s)        having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₃alkylenearyl group or R₁ and R₂ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₁ and R₂        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2    -   3) an alkylene carbonate selected from the group consisting of        ethylene carbonate, propylene carbonate and butylene        carbonate, 4) a polyol capped with acetate or formate wherein        the polyol portion is one or more of ethylene glycol, 1,3        propylene glycol, 1,2 propylene glycol, butylene glycol,        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol, sorbitan, glucose, fructose, galactose and/or        glycerin, 5) an alkylene glycol alkyl ether acetate selected        from the group consisting of dipropylene glycol methyl ether        acetate, tripropylene glycol methyl ether acetate, and        tripropylene glycol butyl ether acetate, 6) isophorone, 7)        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and/or        dimethyl glutarate, 8) dimethylacetamide, dimethylformamide,        dimethyl-2-imidazolidinone 9) hexamethylphosphoramide, 10)        1,2-dimethyloxethane, 2-methoxyethyl ether, 11)        cyclohexylpyrrolidone and/or 12) limonene;        heating said dispersion to a polymerization temperature with or        without a catalyst, held at polymerization temperature until a        molecular weight 1500 to 10000 grams/mol is achieved.

In an embodiment, the process may further comprising neutralizing theone or more monomers with one or more metals, wherein said one or moremetals comprise elemental metals, metal oxides, metal hydroxides, metalalkylates or metal carbonates, or with one or more nitrogen containingcompounds comprising ammonia, ammonium hydroxide, or organoamines.

In an embodiment of the process, the one or more metals in the elementalmetals, metal oxides, metal hydroxides, metal alkylates or metalcarbonates comprise Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo or Ni.

In a variation, the organoamines comprise one or more of mono C₁₋₆amine, di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine, diethanolamine, triethanol amine, monoisopropanol amine, diisopropanol amine,triisopropanol amine, ethylene diamine diethylene triamine, triethylenetetraamine, or tetraethylene pentamine.

In an embodiment, the present invention relates to a process forproducing the composition,

-   -   wherein said process comprises procuring one or more of the        following monomers:    -   aspartic acid, glutamic acid, maleic acid, itaconic acid,        citraconic acid, citric acid, acrylic acid, methacrylic acid,        itaconic acid, and citraconic acid, their anhydrides, and        imides, or their salts;    -   wherein said one or more monomers is/are dispersed into one or        more protic solvents where the molar ratio of protic solvent to        monomer(s) may be any ratio between about 0.5 to 1 and 10 to 1        and/or the weight ratio of the NOSDS to reactive monomer is 10%        to 90% and 90% to 10% which is heated to 120-190° C. to form an        ester    -   wherein the one or more protic solvents are selected from the        group consisting of:    -   1) an alcohol from the family of C₁₋₁₀ alkanols, 2) polyols        selected from the group consisting of trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol, sorbitan,        glucose, fructose, galactose, and glycerin, 3) poly(C₁₋₁₀        alkylene) glycols, 4) alkylene glycols selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, and butylene glycol, 5) isopropylidene        glycerol 6) alkylene glycol alkyl ethers selected from the group        consisting of tripropylene glycol methyl ether, tripropylene        glycol butyl ether, dipropylene glycol butyl ether and        dipropylene glycol butyl ether, 7) ethyl, propyl, or butyl        lactate, 8) an alkanolamine selected from the group consisting        of ethanolamine, diethanolamine, dipropanolamine, methyl        diethanolamine, monoisopropanolamine and triethanolamine and 9)        glycerol carbonate;    -   and heating said dispersion to a polymerization temperature with        or without catalyst, until a molecular weight of 1500 to 10000        g/mol is achieved;    -   and to which one or more aprotic solvents is optionally added        wherein said one or more aprotic solvents comprise 1) dimethyl        sulfoxide 2) dialkyl, diaryl, or alkylaryl sulfoxide(s) having        the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₃ alkylenearyl group or R₁ and R₂ with the sulfur to which        they are attached form a 4 to 7 membered ring wherein R₁ and R₂        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2;    -   3) alkylene carbonates selected from the group consisting of        ethylene carbonate, propylene carbonate and butylene        carbonate, 4) polyols capped with acetate or formate wherein the        polyol is one or more of ethylene glycol, 1,3 propylene glycol,        1,2 propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol, sorbitan,        glucose, fructose, galactose and/or glycerin, 5) alkylene glycol        alkyl ethers acetates selected from the group consisting of        dipropylene glycol methyl ether acetate, tripropylene glycol        methyl ether acetate, and tripropylene glycol butyl ether        acetate, 6) isophorone, 7) dimethylsuccinate, dimethyl adipate,        diethyl glutarate, and/or dimethyl glutarate, 8)        dimethylacetamide, dimethylformamide,        dimethyl-2-imidazolidinone 9) hexamethylphosphoramide, 10)        1,2-dimethyloxethane, 2-methoxyethyl ether, 11)        cyclohexylpyrrolidone and/or 12) limonene.

In a variation of the process, the ester may be further saponifiedgenerating a carboxylic acid salt wherein said salt is derived frommetals, metal hydroxides, metal alkylates, metal carbonates, ammonia,ammonium hydroxide, or organoamines.

In a variation, the metal in the metals, metal hydroxides, metalalkylates, or metal carbonates is Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Moand/or Ni.

In a variation, the organoamines comprise one or more of mono C₁₋₆amine, di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine, diethanolamine, triethanol amine, monoisopropanol amine, diisopropanol amine,triisopropanol amine, ethylene diamine diethylene triamine, triethylenetetraamine, or tetraethylene pentamine.

In a variation, the present invention relates to a process for producingthe composition,

-   -   wherein said process comprises procuring a polymer that        comprises polysuccinimide, polyaspartic acid, polyglutamic acid,        and/or a copolymer of aspartic acid and glutamic acid and/or        salts thereof;    -   wherein    -   said polymer is dispersed within a NOSDS at a % weight ratio of        10:90% to 90:10% of polymer:NOSDS, wherein the NOSDS        comprises a) of one or more protic solvents which are heated to        120-190° C. to form an ester and wherein the one or more protic        solvents are selected from the group consisting of:    -   1) an alcohol from the family of C₁₋₁₀ alkanols, 2) polyols        selected from the group consisting of trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol, sorbitan,        glucose, fructose, galactose, and glycerin, 3) poly(C₁₋₁₀        alkylene) glycols, 4) alkylene glycols selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, and butylene glycol, 5) isopropylidene        glycerol 6) alkylene glycol alkyl ethers selected from the group        consisting of tripropylene glycol methyl ether, tripropylene        glycol butyl ether, dipropylene glycol butyl ether and        dipropylene glycol butyl ether, 7) ethyl, propyl, or butyl        lactate, 8) an alkanolamine selected from the group consisting        of ethanolamine, diethanolamine, dipropanolamine, methyl        diethanolamine, monoisopropanolamine and triethanolamine and 9)        glycerol carbonate.

In a variation, the ester may be saponified.

In an embodiment, the salts may be derived from metals, metalhydroxides, metal alkylates, metal carbonates, ammonia, ammoniumhydroxide, or organoamines and the metal in the metals, metalhydroxides, metal alkylates, or metal carbonates are one or more of Na,K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo or Ni.

In a variation, the organoamines comprise one or more of mono C₁₋₆amine, di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine, diethanolamine, triethanol amine, monoisopropanol amine, diisopropanol amine,triisopropanol amine, ethylene diamine diethylene triamine, triethylenetetraamine, or tetraethylene pentamine.

The following Examples are presented to illustrate certain embodimentsof the present invention:

Example 1

400 grams of ethylene glycol was charged to a vessel, placed understrong agitation and then heated to 60° C. 222.2 grams ofpolyaspartate-potassium salt/90% NVS was then slowly charged to thevessel and mixed until completely dissolved. Once dissolved, the mixturewas placed under high shear agitation by using an overhead mixerequipped with a cowles blade while maintaining the batch temperature at60-80° C. for 1 hour. After one hour the vessel was scaled and a vacuumof 200 mm or less was pulled to remove water. The mixture was cooled to<30° C. and then packaged off in an appropriate container.

Example 2

120 grams of Example 1 was heated to 60° C., placed under agitation andthen 80 grams of propylene glycol was charged to the vessel. Thecombination was mixed for 30 minutes and then cooled to <40° C. andpackaged off.

Example 3

120 grams of Example 1 was heated to 60° C., placed under agitation andthen 80 grams of glycerin were charged to the vessel. The combinationwas mixed for 30 minutes and then cooled to <40° C. and packaged off.

Example 4

120 grams of Example 1 was heated to 60° C., placed under agitation andthen 40 grams of ethylene glycol and 40 grams of tripropylene glycolmonomethyl ether were charged to the vessel. The combination was mixedfor 30 minutes and then cooled to <40° C. and packaged off.

Example 5

450 grams of ethylene glycol was charged to a vessel, placed understrong agitation and then heated to 60° C. 300 grams of apolysuccinimide (5000 average molecular weight) was then slowly chargedto the vessel and mixed until completely dispersed. The mixture was thenheated to 140° C. and held until all particles dissolved (˜1.5 hrs). Themix was then cooled to 50° C. 147 grams of KOH flakes were slowlycharged to the mix at a rate to maintain temperature of 60-80° C. Theformulation was mixed until all KOH flakes (100%) were dissolved. Themix was then cooled to 40° C. and then placed under high shear agitationby using an overhead mixer equipped with a cowles blade whilemaintaining the batch temperature at 60-80° C. for 1 hour. After onehour, an FTIR scan was run to determine if the presence of ester hadbeen eliminated. The mixture was sampled every 30 minutes until tracesof esters had been eliminated. The mixture was cooled to <30° C. andthen packaged off in an appropriate container.

Example 6

58.54 grams of Example 5 was charged to a vessel and then placed understrong agitation and then heated to 60° C. 65.4 grams of ethylene glycolwere then charged to the vessel and mixed for 30 minutes. After 30minutes, the mixture was cooled to 38° C. and then packaged off in anappropriate container.

Example 7

58.54 grams of Example 5 was charged to a vessel and then placed understrong agitation and then heated to 60° C. 35.4 grams of ethylene glycoland 30 grams of dimethyl glutarate were then charged to the vessel andmixed for 30 minutes. After 30 minutes, the mixture was cooled to 38° C.and then packaged off in an appropriate container.

Example 8

58.54 grams of Example 5 was charged to a vessel and then placed understrong agitation and then heated to 60° C. 65.4 grams of glycerin werethen charged to the vessel and mixed for 30 minutes. After 30 minutes,the mixture was cooled to 38° C. and then packaged off in an appropriatecontainer.

Example 9

104.3 grams of Example 5 was charged to a vessel and then placed understrong agitation and then heated to 60° C. 45.7 grams of ethylene glycolwere then charged to the vessel and mixed for 30 minutes. After 30minutes, the mixture was cooled to 38° C. and then packaged off in anappropriate container.

Example 10

183.12 grams of dimethyl sulfoxide was charged to a vessel, placed understrong agitation and then heated to 60° C. 78.48 grams of apolysuccinimide (5000 average molecular weight) was then slowly chargedto the vessel and mixed until completely dispersed. 72.74 grams of DIwater was charged to the vessel and then 49.07 grams of NH4OH/28% wereslowly charged holding the mixture's temperature at 60-80° C. It wasmixed for one hour and then placed under a vacuum of 50 mm with a slightN₂ sparge until distillation ceases. The mix was then cooled to 40° C.and then packaged off in an appropriate container.

Example 11

282.52 grams of dimethyl sulfoxide was charged to a vessel, placed understrong agitation and then heated to 60° C. 146.23 grams of a partialsodium hydroxide neutralized polyacrylic acid (Kemira 5847) was thencharged to the vessel and mixed for 15 minutes. A vacuum of 38 mm wasapplied until distillation ceases. The mix was then cooled to 40° C. andthen packaged off in an appropriate container.

Example 12

150 grams of ethylene glycol, 150 grams of L-aspartic acid and 1.5 gramsof phosphoric acid/85% were charged to a vessel, then placed understrong agitation and then heated to 185° C. After 5 hrs, 64.3 grams ofdistillate were collected and the batch was cooled to 60° C. 97.44 gramsKOH flake (100%) was then slowly charged to the vessel at a rate thatallowed the batch temperature to be 60-80° C. and mixed until completelydissolved. It was then placed under high shear agitation by using anoverhead mixer equipped with a cowles blade while maintaining the batchtemperature at 60-80° C. for 1 hour. After one hour, an FTIR scan wasrun to determine if the presence of ester had been eliminated. Themixture was sampled every 30 minutes until traces of esters had beeneliminated. After the ester peak was eliminated, 281.08 grams ofethylene glycol were charged and the resulting mixture was mixed for 30minutes. The mix was then cooled to 40° C. and then packaged off in anappropriate container.

Example 13

71.58 grams of acetone was charged to a vessel and then 12.48 grams ofmaleic anhydride and 16.49 grams itaconic anhydride and 0.98 grams ofbenzoyl peroxide were charged to the vessel. Very slow agitation wasused until the maleic briquettes were dissolved. The vessel was thensealed and inerted with N₂ and the batch was heated to 60° C. and heldat 55-65° C. for five hours. After five hours, the batch was cooled to35° C. and 43.45 grams of ethylene glycol was charged. A vacuum was thenpulled on the vessel slowly decreasing the pressure based on thedistillation rate while heating the batch back to 55-65° C. Whendistillation ceases, the vacuum was broken with N₂ and then 15.39 gramsof KOH flake (100%) were slowly charged in order to hold temperature at60-80° C. When KOH flakes were completely dissolved, the mix was placedunder high shear agitation by using an overhead mixer equipped with acowles blade while maintaining the batch temperature at 60-80° C. for 1hour. Thereafter the mix was checked using an FTIR scan. The FTIR scanwas run and checked every 30 minutes for the disappearance of the esterpeak. After the ester peak disappeared, 89.63 grams of ethylene glycolwere charged, and the batch was then mixed 30 minutes and cooled to <40°C. and then off-loaded into the appropriate container.

Example 14

45 grams of Example 12 were mixed with 10 grams of N-Yield (a ureaseinhibitor in a non-aqueous liquid), 40 grams of N-Bound (a nitrificationinhibitor in a non-aqueous liquid) and 5 grams of glycerin. Theresulting fluid product was then off-loaded into the appropriatecontainer.

Example 15

99.5 grams of DMSO, 99.5 grams of L-aspartic acid and 1.0 grams ofphosphoric acid/85% were charged to a vessel, then placed under strongagitation and then heated to 155° C. After 4.5 hrs. 28.49 grams ofdistillate were collected and the batch was cooled to 80° C. 85.09 gramsNH₄OH (28%) was then slowly charged to the vessel at a rate that allowedthe batch temperature to be 60-80° C. over a 5 hour period. The reactorwas scaled and heated to 95 C and held for 17 hrs and then checked by IRto insure the ester was eliminated. 352.88 gins of DMSO were charged andthen heated back to 80 C. 68.07 gms of DCD were charge and mixed untilparticles dissolved. The batch was cooled to 35 C and then 17.02 NBPTwere charged and mixed until particles dissolved. 51.05 gms of propyleneglycol were charged and mix 15 minutes. The mixture was then package and50 gms placed in a 50 C oven for 3 days. After 3 days at 50 C, theproduct showed no signs of instability.

Example 16

43.57 grams of polysuccinimide (molecular weight 3000-5000), 119.12grams of ethylene glycol were charged to a reactor, placed underagitation and heated to 140° C. until all particles were solubilized.2.41 grams of zinc oxide were charged while holding temperature at 120°C. until appearance of mixture transitioned from milky to translucent.The reactor was then cooled to 40 C and 19.19 of KOH/45% were slowedcharged while holding the temperature less than 80° C. The product wasthen cooled to <40° C. and packaged off.

Example 17

250 grams of ethylene glycol, 250 grams of L-aspartic acid and 2.94grams of phosphoric acid/85% were charged to a vessel, then placed understrong agitation and then heated to 150° C. After 5 hours no particleswere observed and 67.6 grams of distillate were collected. The batch wascooled to 120° C. and 23.67 grams of magnesium oxide was slowly chargedand dispersed with 15 minutes if agitation. 10.57 grams of distilledwater was then charged to the vessel and the contents were agitateduntil contents cleared in approximately 5.5 hours. The contents of thevessel were then cooled to 60° C., 103.21 grams KOH flake (100%) wasthen slowly charged to the vessel at a rate that allowed the batchtemperature to be maintained at 60-80° C. and mixed until completelydissolved. It was then mixed an additional hour. After one hour, an FTIRscan was run to determine if the presence of ester had been eliminated.The mixture was sampled every 30 minutes until traces of esters had beeneliminated. After the ester peak was eliminated, the batch was cooled to40° C. and then placed under high shear agitation by using rotor statormixer while maintaining the batch temperature at less than 80° C. byusing an ice bath and by slowly increasing the RPM's of the mixer to10,000 over a 1 hour time period. After the high shear mixing, 233.66grams of ethylene glycol were charged and the resulting mixture wasmixed for 30 minutes. The mix was cooled to <40° C. and then packagedoff in an appropriate container.

Example 18

128.46 grams of ethylene glycol, 62.06 grams of L-aspartic acid and 0.99grams of phosphoric acid/85% were charged to a vessel, then placed understrong agitation and heated to 150° C. After 5 hours no particles wereobserved and 16.22 grams of distillate were collected. The batch wascooled to 120° C. and 7.67 grams of zinc oxide was slowly charged anddispersed with 15 minutes if agitation. 1.70 grams of distilled waterwas then charged to the vessel and the contents were agitated until thecontents cleared in approximately 8.5 hours. The contents of the vesselwere then cooled to 60° C., 14.27 grams KOH flake (100%) was then slowlycharged to the vessel at a rate that allowed the batch temperature to bemaintained at 60-80° C. and mixed until completely dissolved. It wasthen mixed an additional hour. After one hour, an FTIR scan was run todetermine if the presence of ester had been eliminated. The mixture wassampled every 30 minutes until traces of esters had been eliminated.After the ester peak was eliminated, the batch was then cooled to <40°C. and then packaged off in an appropriate container.

Example 19

333.9 grams of DMSO were charged to a reactor, placed under agitationand then 477 grams of sorbitol/70% were charged to the reactor. Themixture was then heated to 75° C. and placed under 20 mm of vacuum tostrip out residual water. Once the formation of distillate ceased, themixture was cooled to 40° C. and 611.59 grams of DMSO/sorbitol wererecovered. In a mixing vessel, 71.3 grams of Example #5 were chargedfollowed by 31.1 grams of the DMSO/sorbitol mixture and 31.1 grams ofDMSO. The combination was mixed for 15 minutes and then 16.5 grams ofKOH flakes were slowly charged holding the temperature below 80° C. Theproduct was cooled below 40° C. and packaged.

Example 20

In a reactor, 122.24 grams of L-aspartic acid and 76.77 grams ofpropylene glycol were charged, placed under agitation and heated to 170°C. It was held at 17° C. until all particles disappeared. 199.04 gramsof PG and 14.92 grams of zinc oxide were charged to the reactor whilemaintaining the batch temperature at 120-160° C. After batch appearancetransitioned from milky to translucent, the batch was cooled to 40° C.and 61.81 grams of KOH/45% were slowly charged to reactor whilemaintaining the batch temperature below 80° C. The product was mixed 14hours at 80° C. to saponify all ester linkages. The batch was thencooled to less than 40° C. and packaged

Example 21

In a reactor, charge 450.77 grams glycerin and 300 grams polysuccinimide(3000-5000 molecular weight) and heat to 140° C. and hold until allparticles have reacted/dissolved. Cool to 40° C.

Example 22

In a mixing vessel under agitation, 48.8 grams of Example 21 and 28.6grams of glycerin were charged. Then 22.6 grams of KOH/45% were slowlycharged holding temp less than 80° C. during charge. After charging KOH,hold at 80° C. until ester linkages have been saponified. Cool to lessthan 40° C. and package off.

Example 23

In a mixing vessel under agitation, charge 48.8 grams of Example 22 and28.6 grams of propylene glycol. Slowly charge 22.6 grams of KOH/45%holding temp less than 80° C. during charge. After charging KOH, hold at80° C. until ester linkages have been saponified. Cool to less than 40°C. and package off.

Example 24

60.55 grams of ethylene glycol, 130.01 grams of L-aspartic acid(ethylene glycol/aspartic acid molar ratio of 1:1 and a weight ratio of32% to 68%) and 0.95 grams of phosphoric acid/85% were charged to avessel, then placed under very low agitation and then slowly heated to170° C. over a period of five hours. The rate of temperature rise wasdependent on ability to increase agitation speed as high as productsolids and viscosity would allow so as to not allow the product to burn.After 5 hours no particles were observed and 37.33 grams of distillatewere collected. 279.42 grams of ethylene glycol were charged and thebatch was cooled to 60° C. 49.82 grams KOH flake (100%) was then slowlycharged to the vessel at a rate that allowed the batch temperature to bemaintained at 60-80° C. and mixed until completely dissolved. It wasthen mixed and heated to 80 C and held an additional hour. The mix wascooled to <40° C. and then packaged off in an appropriate container.

Example 25

48.4 grams of ethylene glycol were charge to a reactor, placed underagitation and a nitrogen sparge and heated to 90° C. 113.7 grams of apolysuccinimide (molecular weight 3000-5000) were slowly added to thereactor while increasing the agitation as needed and holding thetemperature between 80 and 100° C. The very viscous product was thenheated to 120° C. and 37.9 grams of addition polysuccinimide (molecularweight 3000-5000) were slowly charged to the reactor raising the molarratio of PSI to Ethylene Glycol to 1:0.5 and the weight ratio 75.8% to24.2%. The agitation was increased as product viscosity allowed. After30 minutes the batch temperature was increased to 150° C. After 60minutes at 150° C., all particles were dissolved. 384.48 grams ofethylene glycol were charged and the batch was cooled to 60 C. 63.46grams of KOH (100%) were slowly charged to the reactor while maintainingthe batch temperature 60-80° C. utilizing a cooling bath to assist inremoving the heat from the exothermic neutralization. After all the KOHhad been charged and was dissolved, the batch temperature was held at80° C. under strong agitation for 3 hours. The batch was then cooled to<40 C and packaged off in an appropriate container.

Example 26

A dye was required in order to determine effectiveness of coating

20 grams of each Example was placed under agitation and 0.4 grams of a20% FD&C Blue #1 in a solvent was added to the 20 grams of each example.Each example was mixed for 15 minutes after addition of dye. Included inthe testing were two aqueous commercial products,

Avail & P-Max Sample ID Prepared for Coating Test

Example ID Sample ID Example 2 Sample 1 Example 3 Sample 2 Example 4Sample 3 Example 6 Sample 4 Example 7 Sample 5 Example 8 Sample 6Example 9 Sample 7 Example 10 Sample 8 Example 11 Sample 9 Example 12Sample 10 Example 13 Sample 11 Example 14 Sample 12 Example 15 Sample 13Example 16 Sample 14 Example 17 Sample 15 Example 18 Sample 16 Example19 Sample 17 Example 20 Sample 18 Avail Sample 19 P-Max Sample 20Example 23 Sample 21 Example 24 Sample 22 Example 25 Sample 23

Example 27

200 grams of a technical grade of DAP was charged to a glass 1000 mlbeaker. The beaker was then placed under an overhead agitator with ananchor agitator blade. The height of the beaker was adjusted such thatthe bottom of the anchor agitator blade was close to the bottom of theglass beaker. The RPM of the overhead stirrer was adjusted to 200 RPM'sand the DAP was agitated for 30 seconds. After 30 seconds, a 2.0 gram ofa sample of Example 21 was charged within 10 seconds. A stopwatch wasused for timing to complete coating. (Visually: when 95% of DAPparticles were colored blue). This was repeated for each of the testedsamples from Example 26.

After coating, the 200 grams of coated DAP was poured in a one quart jarand 200 grams of weight were placed on top of each sample in the quartjar. After setting for 48 hours, the weight was removed and a lid wasplaced on each quart jar. Each jar was then inverted and rated forflowability. If the contents of a jar did not flow in 5 minutes, awooden handle of a 4 inch spatula was used to tap the jar to encourageflow. Flow rating is as follows:

Rating Action after inversion 1 Instant flow 2 >70% flow in 1 minute3 >70% flow in 1-3 minutes 4 >70% flow in 3-5 minutes 5 >70% flow after1-2 taps 6 >70% flow after 3-4 taps 7 >70% flow after 5-6 taps 8 40-60%flow after 5-6 taps 9 20-40% flow after 5-6 taps 10 0-20% flow after 5-6taps

Sample Performance on DAP

Time to coat 48 hour Sample ID in seconds pack test Sample 1 20 4 Sample2 24 5 Sample 3 20 3 Sample 4 15 2 Sample 5 27 3 Sample 6 26 4 Sample 718 3 Sample 8 14 2 Sample 9 27 3 Sample 10 34 5 Sample 11 32 4 Sample 1225 4 Sample 13 24 4 Sample 14 24 4 Sample 15 27 3 Sample 16 29 5 Sample17 30 6 Sample 18 21 2 Sample 19* 51 10 Sample 20* 56 10 Sample 21 32 4Sample 22 28 4 Sample 23 28 4 *Difficult to determine coating time asthe color was streaky and not continuous.

Example 27

200 grams of a technical grade of magnesium sulfate was charged to aglass 1000 ml beaker. The beaker was then placed under an overheadagitator with an anchor agitator blade. The height of the beaker wasadjusted such that the bottom of the anchor agitator blade was close tothe bottom of the glass beaker. The RPM of the overhead stirrer wasadjusted to 200 RPM's and the magnesium sulfate was agitated for 30seconds. After 30 seconds, a 2.0 gram of a sample of Example 21 wascharged within 10 seconds. A stopwatch was used for timing to completecoating. (Visually: when 95% of magnesium sulfate particles were coloredblue). This was repeated for each of samples tested.

After coating, the 200 grams of coated magnesium sulfate was poured in aone quart jar and 200 grams of weight were placed on top of each samplein the quart jar. After setting for 48 hours, the weight was removed anda lid was placed on each quart jar. Each jar was then inverted and ratedfor flowability. If the contents of a jar did not flow in 5 minutes, awooden handle of a 4 inch spatula was used to tap the jar to encourageflow. Flow rating is as follows:

Rating Action after inversion 1 Instant flow 2 >70% flow in 1 minute3 >70% flow in 1-3 minutes 4 >70% flow in 3-5 minutes 5 >70% flow after1-2 taps 6 >70% flow after 3-4 taps 7 >70% flow after 5-6 taps 8 40-60%flow after 5-6 taps 9 20-40% flow after 5-6 taps 10 0-20% flow after 5-6taps

Sample Performance on Magnesium Sulfate

Time to coat in 48 hour Sample ID seconds pack test Sample 1 22 4 Sample2 23 5 Sample 3 20 4 Sample 4 18 2 Sample 5 27 3 Sample 6 29 3 Sample 717 3 Sample 8 14 2 Sample 9 29 3 Sample 10 31 6 Sample 11 33 4 Sample 1226 4 Sample 13 36 4 Sample 14 25 5 Sample 15 28 3 Sample 16 29 5 Sample17 30 6 Sample 18 18 2 Sample 19* 54 10 Sample 20* 58 10 Sample 21 33 4Sample 22 28 3 Sample 23 28 3 *Difficult to determine coating time asthe color was streaky and not continuous.

Example 28

120 grams of prilled urea, 20 grams of fertilizer grade potassiumsulfate, 40 grams of fertilizer grade diammonium phosphate, 10 grams offertilizer grade zinc sulfite and 10 grams of fertilizer grade ironsulfate were charged to a glass 1000 ml beaker. The beaker was thenplaced under an overhead agitator with an anchor agitator blade. Theheight of the beaker was adjusted such that the bottom of the anchoragitator blade was close to the bottom of the glass beaker. The RPM ofthe overhead stirrer was adjusted to 200 RPM's and the contents of thecompounded fertilizer were agitated for 30 seconds. After 30 seconds, a2.0 gram of each sample to be tested was charged within 10 seconds. Astopwatch was used for timing to complete coating. (Visually: when 95%of magnesium sulfate particles were colored blue). This was repeated foreach of the samples to be tested.

After coating, the 200 grams of coated compounded fertilizer was pouredin a one quart jar and 200 grams of weight were placed on top of eachsample in the quart jar. After setting for 48 hours, the weight wasremoved and a lid was placed on each quart jar. Each jar was theninverted and rated for flowability. If the contents of a jar did notflow in 5 minutes, a wooden handle of a 4 inch spatula was used to tapthe jar to encourage flow. Flow rating is as follows:

Time to coat 48 hour Sample ID in seconds pack test Sample 1 18 3 Sample2 22 5 Sample 3 23 3 Sample 4 14 2 Sample 5 26 3 Sample 6 28 5 Sample 720 3 Sample 8 18 2 Sample 9 25 3 Sample 10 32 5 Sample 11 28 4 Sample 1225 4 Sample 13 26 3 Sample 14 27 4 Sample 15 27 3 Sample 16 28 5 Sample17 28 6 Sample 18 15 2 Sample 19* 47 8 Sample 20* 48 9 Sample 21 29 5Sample 22 28 4 Sample 23 29 5 *Difficult to determine coating time asthe color was streaky and not continuous

Rating Action after inversion 1 Instant flow 2 >70% flow in 1 minute3 >70% flow in 1-3 minutes 4 >70% flow in 3-5 minutes 5 >70% flow after1-2 taps 6 >70% flow after 3-4 taps 7 >70% flow after 5-6 taps 8 40-60%flow after 5-6 taps 9 20-40% flow after 5-6 taps 10 0-20% flow after 5-6taps

Example 29

100 grams of uncoated “tall” fescue grass seeds was charged to a glass1000 ml beaker. The beaker was then placed under an overhead agitatorwith an anchor agitator blade. The height of the beaker was adjustedsuch that the bottom of the anchor agitator blade was close to thebottom of the glass beaker. The RPM of the overhead stirrer was adjustedto 100 RPM's and the seeds were agitated for 30 seconds. After 30seconds, a 2.0 gram of a sample was charged within 10 seconds. The seedswere agitated until 95% of the seeds were coated.

After coating, the 1 gram of coated seeds was added to 150 ml glassbeaker in a manner to insure the seeds were equally distributed on thebottom of the beaker. The top of the beaker was sealed with a plasticwrap and placed in an dark environment at 30 C. The beaker was checkedat 7, 14 and 21 days for signs of germination and rated for % of seedsthat germinated.

After 60 days, the plastic wrap covering was slit and a prepared Contectest strip was inserted and placed just above the seed to test forpresence of mold and mildew.

% germination Rating of seeds 0 None 1  0-5% 2  5-10% 3 10-20% 4 20-30%5  >30%

Mold/mildew Sample ID 7 days 14 days 21 days after 60 days Sample 1 0 00 No Sample 2 0 0 0 No Sample 3 0 0 0 No Sample 4 0 0 0 No Sample 7 0 00 No Sample 8 0 0 0 No Sample 9 0 0 0 No Sample 10 0 0 0 No Sample 14 00 0 No Sample 18 0 0 0 No Sample 19 0 1 2 Yes Sample 20 0 1 2 Yes

The below table 1 summarizes the compositions that occur in each of theexamples. The presence of an “X” in table 1 means that the particularexample composition contains that particular component.

TABLE 1 Example No. DMSO Glycerin TPGME Sorbitol DMG PG DPG EG PC TT DDAT DMA 1 X 2 X X 3 X X 4 X X 5 X 6 X 7 X X 8 X X 9 X 10 X 11 X 12 X 13 X14 X X X 15 X 16 X 17 X 18 X 19 X X 20 X 21 X 22 X 23 X X 24 X 25 XDMSO—dimethylsulfoxide PG—propylene glycol DPG—dipropylene glycolDMG—Dimethyl Gluterate TPGME—tripropylene glycol methyl etherEG—ethylene glycol

Samples from Examples 1-25 were evaluated for safety and environmentalproperties and the results are shown in the below Table 2:

TABLE 2 Human Aquatic Health Flash Toxicity Sample # Rating Point ° F.Rating Ex 1 1.0 >145° Low Ex 2 1.0 >145° Low Ex 3 1.0 >145° Low Ex 41.0 >145° Low Ex 5 1.0 >145° Low Ex 6 1.0 >145° Low Ex 7 1.0 >145° LowEx 8 1.0 >145° Low Ex 9 1.0 >145° Low Ex 10 1.0 >145° Low Ex 111.0 >145° Low Ex 12 1.0 >145° Low Exl3 1.0 >145° Low Ex 14 1.0 >145° LowEx 15 1.0 >145° Low Ex 16 1.0 >145° Low Ex 17 1.0 >145° Low Ex 181.0 >145° Low Ex 19 1.0 <145° Low Ex 20 1.0 >145° Low Ex 21 1.0 >145°Low Ex 22 1.0 >145° Low Ex 23 1.0 >145° Low Ex 24 1.0 >145° Low Ex 251.0 >145° LowThe Human Health rating is based on (Hazardous Materials InformationSystem) rating on Health of any organo solvent component >2:The Flash Point is based on flash point of any organo solvent component>5%The Aquatic Toxicity Rating is based on any organo solvent component atany level

The following references are incorporated by reference in theirentireties.

4,839,461 Boehmke 4,172,072 Ashmead 4,799,953 Danzig 4,813,997Kinnersley 4,863,506 Young 5,059,241 Young 5,047,078 Gill 5,350,735Kinnersley 5,593,947 Kinnersley 5,783,523 Koskan 5,814,582 Koskan6,753,395 Sanders 6,756,461 Sanders 6,818,039 Sanders 8,043,995 Sanders8,016,907 Sanders 8,025,709 Sanders 5,994,265 Barclay 7,001,869 Johnson6,557,298 Obert

It is contemplated and therefore within the scope of the presentinvention that any feature that is described above can be combined withany other feature that is described above. When mixtures, formulationsand/or compositions are discussed, it should be understood that thosemixtures, formulations and/or compositions are contemplated as beingparts of bigger mixtures, formulations and/or compositions. Further, ifa composition is enumerated, methods using and methods of making thatcomposition are contemplated and within the scope of the presentinvention. When a range is discussed, it is contemplated and thereforewithin the scope of the invention that any number that falls within thatrange is contemplated as an end point generating a plurality ofsub-ranges within that range. For example if a range of 1-10 is given,2, 3, 4, 5, 6, 7, 8, and 9 are contemplated as end points to generate asub-range that fit within the scope of the enumerated range. Moreover,it should be understood that the present invention contemplates minormodifications that can be made to the compositions and methods of thepresent invention. In any event, the present invention is defined by thebelow claims.

1-12. (canceled)
 13. A composition comprising a) one or more Poly(organic acids), [P(OA)]s, and/or their salts, b) a Non-aqueous OrganoSolvent Delivery System (NOSDS), c) one or more inhibitors, and d) oneor more members selected from the group consisting of i) one or morefertilizers selected from the group consisting of (1) fertilizer solidsand (2) liquid fertilizers and ii) seeds, wherein the NOSDS is thedelivery formulation for delivering the one or more [P(OA)]s and/ortheir salts to said fertilizers and seeds, wherein the NOSDS iscomprises one or more members selected from the group consisting of i)protic solvents and ii) aprotic solvents, wherein the one or more proticsolvents is selected from the group consisting of (1) one or morealcohols selected from the group consisting of C₁₋₁₀ alcohol, (2) one ormore polyols selected from the group consisting of trimethylol propane,trimethylol ethane, pentaerythritol, sorbitol and sorbitan, glucose,fructose, galactose, and glycerin, (3) one or more poly(C₁₋₁₀ alkylene)glycols, (4) one or more alkylene glycols selected from the groupconsisting of ethylene glycol, 1,3 propylene glycol, 1,2 propyleneglycol, and butylene glycol, (5) isopropylidene glycerol, (6) one ormore alkylene glycol alkyl ethers selected from the group consisting oftripropylene glycol methyl ether, tripropylene glycol butyl ether,dipropylene glycol methyl ether and dipropylene glycol butyl ether, (7)one or more lactates selected from the group consisting of ethyl,propyl, and butyl lactate, (8) one or more alkanolamine selected fromthe group consisting of ethanolamine, diethanolamine, dipropanolamine,methyl diethanolamine, monoisopropanolamine and triethanolamine, and (9)glycerol carbonate, and wherein one or more aprotic solvents is selectedfrom the group consisting of (1) dimethyl sulfoxide, (2) one or moremembers selected from the group consisting of dialkyl sulfoxide, diarylsulfoxide, and alkylaryl sulfoxides having the formula:R₁S(O)_(x)R₂  (a) wherein R₁ and R₂ are each independently a C₁₋₆ alkylgroup, an aryl group, or C₁₋₃ alkylenearyl group, or R₁ and R₂ with thesulfur to which they are attached form a 4 to 7 membered ring wherein R₁and R₂ together are a C₁₋₆ alkylene group which optionally contains oneor more atoms selected from the group consisting of O, S, Se, Te, N, andP in the ring and x is 1 or 2, (3) one or more alkylene carbonatesselected from the group consisting of ethylene carbonate, propylenecarbonate and butylene carbonate, (4) a polyol capped with acetate orformate wherein the one or more polyol portion is selected from thegroup consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propyleneglycol, butylene glycol, trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, andglycerin, (5) one or more alkylene glycol alkyl ether acetates selectedfrom the group consisting of dipropylene glycol methyl ether acetate,tripropylene glycol methyl ether acetate, and tripropylene glycol butylether acetate, (6) isophorone, (7) one or more alkyl diesters selectedfrom the group consisting of dimethylsuccinate, dimethyl adipate,diethyl glutarate, and dimethyl glutarate, (8) one or more membersselected from the group consisting of dimethylacetamide,dimethylformamide, dimethyl-2-imidazolidinone, (9)hexamethylphosphoramide, (10) 1,2-dimethyloxyethane, (11) 2-methoxyethylether, (12) cyclohexylpyrrolidone, and (13) limonene, wherein said oneor more inhibitors is selected from the group consisting of one or morenitrification inhibitors and one or more urease inhibitors, wherein theone or more nitrification inhibitors is selected from the groupconsisting of (1) 2-chloro-6-trichloromethylpyridine, (2)4-amino-1,2,4-6-triazole-HCl, (3) 2,4-diamino-6-trichloromethyltriazineCL-1580, (4) dicyandiamide, (5) thiourea, (6) 1-mercapto-1,2,4-triazole,(7) 2-amino-4-chloro-6-methylpyrimidine, and (8) dimethyl pyrazolephosphate, and wherein the one or more urease inhibitors is selectedfrom the group consisting of: (1) alkyl thiophosphoric triamides, (2)acetohydroxamic acid and its derivatives, (3) phosphodiamidate, (4)phosphoric triamides, (5) thiophosphoric triamides, and (6) alkylatedthiophosphoric triamides, wherein the alkylated thiophosphoric triamideshas one or more alkyl groups that independently contain between 1 and 6carbon atoms.
 14. The composition of claim 13, wherein a method ofadding one or more said inhibitors to said fertilizers comprises a) oneor more nitrification inhibitors and/or one or more urease inhibitorsdissolved within said organic liquid solvating system, b) optionallyadding one or more dispersed nitrification inhibitors and/or dispersedurease inhibitors to the organic liquid solvating system and/or c)optionally adding one or more dispersed nitrification inhibitors and/ordispersed urease inhibitors to the fertilizer solids and/or liquidfertilizers.
 15. The composition of claim 13, wherein the one or moreurease inhibitors comprises N-(n-butyl) thiophosphoric triamide.
 16. Thecomposition of claim 13, wherein said [P(OA)]s and/or their saltscomprise one or more members selected from the group consisting of a)monomer, b) homopolymer, c) a copolymer and d) a terpolymer wherein said[P(OA)]s composition comprise one or more members selected from thegroup consisting of aspartic acid, glutamic acid, maleic acid, itaconicacid, citraconic acid, citric acid, acrylic acid, methacrylic acid,itaconic acid, and citraconic acid, their C₁₋₆ esters, anhydrides,imides, and salts.
 17. The composition of claim 13, wherein thecomposition of the NOSDS and [P(OA)]s is substantially free of water.18. The composition of claim 13, wherein the composition of the liquidformulation comprises salts of [P(OA)]s wherein the [P(OA)]s are reactedwith one or more members selected from the group consisting of metals,metal hydroxides, metal alkylates, metal carbonates, ammonia, ammoniumhydroxide and organoamines.
 19. The composition of claim 18, wherein themetals cations comprise one or more members selected from the groupconsisting of Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo or Ni.
 20. Thecomposition of claim 18, wherein the organoamines comprise one or moremembers selected from the group consisting of mono C₁₋₆ amine, di C₁₋₆amine, tri C₁₋₆ amine, monoethanolamine, diethanolamine,triethanolamine, monoisopropanol amine, diisopropanolamine,triisopropanolamine, ethylenediamine, diethylene triamine, triethylenetetraamine, and tetraethylene pentamine.
 21. The composition of claim13, wherein the fertilizer solids comprise macronutrients andmicronutrients wherein the macronutrients comprise one or more membersselected from the group consisting of a) urea, b) manure, c)monoammonium phosphate and d) diammonium phosphate and wherein saidmicronutrients salts comprise one or more metal cations selected fromthe group consisting of Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo or Ni.
 22. Thecomposition of claim 13, further comprising one or more members selectedfrom the group consisting of: a) surfactants, b) buffers, c)fragrance/odor masking agents, d) colorants, e) micro-nutrients, f)dispersed urease inhibitors, g) dispersed nitrification inhibitors, h)pesticides, i) fungicides, j) herbicides, k) insecticides and l) flowmodifiers
 23. The composition of claim 22, wherein the one or morefungicides is selected from the group consisting of azoxystrobin,bacillus lichenformis, boscalid, captan, chloroneb, chlorothalonil,ethazole (etridiazole), fenarimol, fludioxonil, flutolanil,fosetyl-aluminum, iprodione, mancozeb, mefenoxam, myclobutanil,potassium phosphite, polyoxin D, propamocarb, propiconazole,pyraclostrobin, tebuconazole, thiophanate-methyl, thiram, triadimefon,trifloxystrobin and vinclozolin, wherein the one or more herbicides isselected from the group consisting of 2,4-D, 2,4-DB, acetochlor,acifluorfen, alachlor, ametryn, atrazine, aminopyralid, benefin,bensulfuron, bensulide, bentazon, bromacil, bromoxynil, butylate,carfentrazone, chlorimuron, chlorsulfuron, clethodim, clomazone,clopyralid, cloransulam, cycloate, DCPA, desmedipham, dicamba,dichlobenil, diclofop, diclosulam, diflufenzopyr, dimethenamid, diquat,diuron, DSMA, endothall, EPTC, ethalfluralin, ethofumesate, fenoxaprop,fluazifop-P, flucarbazone, flufenacet, flumetsulam, flumiclorac,flumioxazin, fluometuron, fluroxypyr, fomesafen, foramsulfuron,glufosinate, glyphosate, halosulfuron, hexazinone, imazamethabenz,imazamox, imazapic, imazaquin, imazethapyr, isoxaben, isoxaflutole,lactofen, linuron, MCPA, MCPB, mesotrione, metolachlor-s, metribuzin,metsulfuron, molinate, MSMA, napropamide, naptalam, nicosulfuron,norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat, pelargonicacid, pendimethalin, phenmedipham, picloram, primisulfuron, prodiamine,prometryn, pronamide, propanil, prosulfuron, pyrazon, pyrithiobac,quinclorac, quizalofop, rimsulfuron, sethoxydim, siduron, simazine,sulfentrazone, sulfometuron, sulfosulfuron, tebuthiuron, terbacil,thiazopyr, thifensulfuron, thiobencarb, tralkoxydim, triallate,triasulfuron, tribenuron, triclopyr, trifluralin and triflusulfuron, andwherein the one or more insecticides selected from the group consistingof bifenthrin, cypermethrin, permethrin, piperonyl butoxide,lambda-cyhalothrin, (s)-methoprene, deltamethrin, permethrin,esfenvalerate, pyriproxyfen, fipronil, etofenprox, cyphenothrin,carbofuran, chlorpoyrifos, disulfoton, fenvalerate, ethoprop, fonofos,malathion, permethrin, phorate, tefluthrin, terbufos, trimethacarb,allicin, anabasine, azadirachtin, carvacrol, d-limonene, matrine,nicotine, nornicotine, oxymatrine, pyrethrins, cinerins, jasmolin,quassia, rhodojaponin, rotenone, ryania, sabadilla, sanguinarine,triptolide, carbamate insecticides, benzofuranyl methylcarbamateinsecticides, dimethylcarbamate insecticides, oxime carbamateinsecticides, phenyl methylcarbamate insecticides, dinosam, DNOC,fluorine insecticides, formamidine insecticides, amitraz, chlordimeform,formetanate, formparanate, medimeform, semiamitraz.
 24. A compositioncomprising a) one or more Poly (organic acids), [P(OA)]s, and/or theirsalts and b) a Non-aqueous Organo Solvent Delivery System (NOSDS), c)one or more inhibitors and d) one or more ureas selected from the groupconsisting of i) urea solids and ii) mixtures of liquid ureas, whereinthe NOSDS and the one or more [P(OA)]s and/or their salts are thedelivery formulation for delivering the one or more [P(OA)]s and/ortheir salts to the surface of urea solids and/or to mixtures of liquidureas, wherein said NOSDS comprises one or more members from the groupconsisting of i) protic solvents and ii) aprotic solvents wherein theone or more protic solvents are selected from the group consistingof:
 1. one or more alcohols selected from the group consisting of C₁₋₁₀alcohol,
 2. one or more polyols selected from the group consisting oftrimethylol propane, trimethylol ethane, pentaerythritol, sorbitol andsorbitan, glucose, fructose, galactose, and glycerin,
 3. one or morepoly(C₁₋₁₀ alkylene) glycols,
 4. one or more alkylene glycols selectedfrom the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2propylene glycol, and butylene glycol,
 5. isopropylidene glycerol, 6.one or more alkylene glycol alkyl ethers selected from the groupconsisting of tripropylene glycol methyl ether, tripropylene glycolbutyl ether, dipropylene glycol methyl ether and dipropylene glycolbutyl ether,
 7. one or more lactates selected from the group consistingof ethyl, propyl, and butyl lactate,
 8. one or more alkanolamineselected from the group consisting of ethanolamine, diethanolamine,dipropanolamine, methyl diethanolamine, monoisopropanolamine andtriethanolamine, and
 9. glycerol carbonate, and wherein one or moreaprotic solvents is selected from the group consisting of (1) dimethylsulfoxide, (2) one or more members selected from the group consisting ofdialkyl sulfoxide, diaryl sulfoxide, and alkylaryl sulfoxides having theformula:R₁S(O)_(x)R₂ wherein R₁ and R₂ are each independently a C₁₋₆ alkylgroup, an aryl group, or C₁₋₃ alkylenearyl group, or R₁ and R₂ with thesulfur to which they are attached form a 4 to 7 membered ring wherein R₁and R₂ together are a C₁₋₆ alkylene group which optionally contains oneor more atoms selected from the group consisting of O, S, Se, Te, N, andP in the ring and x is 1 or 2, (3) one or more alkylene carbonatesselected from the group consisting of ethylene carbonate, propylenecarbonate and butylene carbonate, (4) a polyol capped with acetate orformate wherein the one or more polyol portion is selected from thegroup consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propyleneglycol, butylene glycol, trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, andglycerin, (5) one or more alkylene glycol alkyl ether acetates selectedfrom the group consisting of dipropylene glycol methyl ether acetate,tripropylene glycol methyl ether acetate, and tripropylene glycol butylether acetate, (6) isophorone, (7) one or more alkyl diesters selectedfrom the group consisting of dimethylsuccinate, dimethyl adipate,diethyl glutarate, and dimethyl glutarate, (8) one or more membersselected from the group consisting of dimethylacetamide,dimethylformamide, dimethyl-2-imidazolidinone, (9)hexamethylphosphoramide, (10) 1,2-dimethyloxyethane, (11) 2-methoxyethylether, (12) cyclohexylpyrrolidone, and (13) limonene, wherein said oneor more inhibitors is selected from the group consisting of one or morenitrification inhibitors and one or more urease inhibitors, wherein theone or more nitrification inhibitors is selected from the groupconsisting of (1) 2-chloro-6-trichloromethylpyridine, (2)4-amino-1,2,4-6-triazole-HCl, (3) 2,4-diamino-6-trichloromethyltriazineCL-1580, (4) dicyandiamide, (5) thiourea, (6) 1-mercapto-1,2,4-triazole,(7) 2-amino-4-chloro-6-methylpyrimidine, and (8) dimethyl pyrazolephosphate, and wherein the one or more urease inhibitors is selectedfrom the group consisting of: (1) alkyl thiophosphoric triamides, (2)acetohydroxamic acid and its derivatives, (3) phosphodiamidate, (4)phosphoric triamides, (5) thiophosphoric triamides, and (6) alkylatedthiophosphoric triamides, wherein the alkylated thiophosphoric triamideshas one or more alkyl groups that independently contain between 1 and 6carbon atoms.
 25. The composition of claim 24, wherein a method ofadding one or more said inhibitors to said fertilizers comprises a) oneor more nitrification inhibitors and/or one or more urease inhibitorsdissolved within said organic liquid solvating system, b) optionallyadding one or more dispersed nitrification inhibitors and/or dispersedurease inhibitors to the organic liquid solvating system and/or c)optionally adding one or more dispersed nitrification inhibitors and/ordispersed urease inhibitors to the fertilizer solids and/or liquidfertilizers.
 26. The composition of claim 24, wherein the one or moreurease inhibitors comprises N-(n-butyl) thiophosphoric triamide.
 27. Thecomposition of claim 24, wherein said [P(OA)]s and/or their saltscomprise one or more members selected from the group consisting of a)monomer, b) homopolymer, c) a copolymer and d) a terpolymer wherein said[P(OA)]s composition comprise one or more members selected from thegroup consisting of aspartic acid, glutamic acid, maleic acid, itaconicacid, citraconic acid, citric acid, acrylic acid, methacrylic acid,itaconic acid, and citraconic acid, their C₁₋₆ esters, anhydrides,imides, and salts.
 28. The composition of claim 24, wherein thecomposition of the NOSDS and [P(OA)]s is substantially free of water.29. The composition of claim 24, wherein the composition comprises saltsof [P(OA)]s, wherein the [P(OA)]s are reacted with one or more membersselected from the group consisting of metals, metal hydroxides, metalalkylates, metal carbonates, ammonia, ammonium hydroxide andorganoamines.
 30. The composition of claim 29, wherein the metalscations comprise one or more members selected from the group consistingof Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo or Ni.
 31. The composition ofclaim 29, wherein the organoamines comprise one or more members selectedfrom the group consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆amine, monoethanolamine, diethanolamine, triethanolamine,monoisopropanol amine, diisopropanolamine, triisopropanolamine,ethylenediamine, diethylene triamine, triethylene tetraamine, andtetraethylene pentamine.
 32. The composition of claim 24, furthercomprising one or more members selected from the group consisting of: a)surfactants, b) buffers, c) fragrance/odor masking agents, d) colorants,e) micro-nutrients, f) dispersed urease inhibitors, g) dispersednitrification inhibitors, h) pesticides, i) fungicides, j) herbicides,k) insecticides and l) flow modifiers wherein the one or more fungicidesis selected from the group consisting of azoxystrobin, bacilluslichenformis, boscalid, captan, chloroneb, chlorothalonil, ethazole(etridiazole), fenarimol, fludioxonil, flutolanil, fosetyl-aluminum,iprodione, mancozeb, mefenoxam, myclobutanil, potassium phosphite,polyoxin D, propamocarb, propiconazole, pyraclostrobin, tebuconazole,thiophanate-methyl, thiram, triadimefon, trifloxystrobin andvinclozolin, wherein the one or more herbicides is selected from thegroup consisting of 2,4-D, 2,4-DB, acetochlor, acifluorfen, alachlor,ametryn, atrazine, aminopyralid, benefin, bensulfuron, bensulide,bentazon, bromacil, bromoxynil, butylate, carfentrazone, chlorimuron,chlorsulfuron, clethodim, clomazone, clopyralid, cloransulam, cycloate,DCPA, desmedipham, dicamba, dichlobenil, diclofop, diclosulam,diflufenzopyr, dimethenamid, diquat, diuron, DSMA, endothall, EPTC,ethalfluralin, ethofumesate, fenoxaprop, fluazifop-P, flucarbazone,flufenacet, flumetsulam, flumiclorac, flumioxazin, fluometuron,fluroxypyr, fomesafen, foramsulfuron, glufosinate, glyphosate,halosulfuron, hexazinone, imazamethabenz, imazamox, imazapic, imazaquin,imazethapyr, isoxaben, isoxaflutole, lactofen, linuron, MCPA, MCPB,mesotrione, metolachlor-s, metribuzin, metsulfuron, molinate, MSMA,napropamide, naptalam, nicosulfuron, norflurazon, oryzalin, oxadiazon,oxyfluorfen, paraquat, pelargonic acid, pendimethalin, phenmedipham,picloram, primisulfuron, prodiamine, prometryn, pronamide, propanil,prosulfuron, pyrazon, pyrithiobac, quinclorac, quizalofop, rimsulfuron,sethoxydim, siduron, simazine, sulfentrazone, sulfometuron,sulfosulfuron, tebuthiuron, terbacil, thiazopyr, thifensulfuron,thiobencarb, tralkoxydim, triallate, triasulfuron, tribenuron,triclopyr, trifluralin and triflusulfuron, and wherein the one or moreinsecticides selected from the group consisting of bifenthrin,cypermethrin, permethrin, piperonyl butoxide, lambda-cyhalothrin,(s)-methoprene, deltamethrin, permethrin, esfenvalerate, pyriproxyfen,fipronil, etofenprox, cyphenothrin, carbofuran, chlorpoyrifos,disulfoton, fenvalerate, ethoprop, fonofos, malathion, permethrin,phorate, tefluthrin, terbufos, trimethacarb, allicin, anabasine,azadirachtin, carvacrol, d-limonene, matrine, nicotine, nornicotine,oxymatrine, pyrethrins, cinerins, jasmolin, quassia, rhodojaponin,rotenone, ryania, sabadilla, sanguinarine, triptolide, carbamateinsecticides, benzofuranyl methylcarbamate insecticides,dimethylcarbamate insecticides, oxime carbamate insecticides, phenylmethylcarbamate insecticides, dinosam, DNOC, fluorine insecticides,formamidine insecticides, amitraz, chlordimeform, formetanate,formparanate, medimeform, semiamitraz;